CN106299460B - 18650 battery cores of high-energy density and preparation method thereof - Google Patents
18650 battery cores of high-energy density and preparation method thereof Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to field of batteries, disclose a kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；The diaphragm is PP or PE material；The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is the mixture of at least one of succinic anhydride, fluorinated ethylene carbonate and vinylene carbonate.18650 battery cores of the invention select specific positive and negative pole material cooperation, have very high energy density, and overcome many technological deficiencies during the preparation process, really are able to realize volume production.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of 18650 battery cores of high-energy density and preparation method thereof.
Background technique
18650 be the founder of lithium ion battery, a kind of standard that Japanese Sony Corporation's current year fixs to save cost
Property lithium ion battery model, wherein 18 indicate diameters be 18mm, 65 indicate length be 65mm, 0 is expressed as cylindrical battery.Often
18650 batteries seen are divided into lithium ion battery, ferric phosphate lithium cell.Lithium ion battery voltage is 3.6V and 4.2V, LiFePO4
Cell voltage is 3.2V, and capacity is usually 1200mAh-3000mAh, and common capacity is 2200mAh-3600mAh.
Material and the system collocation of now flourishing with pure electric automobile, existing 18650 battery cannot
It is not able to satisfy the demand to energy density of electric car, battery itself must be improved to improve the course continuation mileage of electric car
Energy density, therefore need to develop a 18650 batteries suitable for electric automobile power battery.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of 18650 battery cores of high-energy density and its preparation sides
Method.18650 battery cores of the invention select specific positive and negative pole material cooperation, have very high energy density, and preparing
Many technological deficiencies are overcome in journey, really are able to realize volume production.
The specific technical proposal of the invention is: a kind of 18650 battery cores of high-energy density, including shell, positive plate, cathode
Piece, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of the negative electrode tab
For copper foil, negative electrode active material is silicon based composite material；The diaphragm is PP or PE material；The solute of the electrolyte is hexafluoro
Lithium phosphate and di-oxalate lithium borate, the solvent of electrolyte are at least one of succinic anhydride, fluorinated ethylene carbonate and carbonic acid
The mixture of vinylene.
The present invention selects nickel cobalt lithium aluminate and silicon based composite material respectively as positive and negative anodes active material, with it is above-mentioned every
After film, electrolyte cooperation, energy density with higher.But huge body can occur in charge and discharge process for silicon-based anode
Product variation, leads to capacity attenuation quickly.So can use in batches without producer up to now, this invention takes many kinds of measures
The volume expansion of silicon materials is inhibited, and improves the electrical contact between silicon particle, so that it is negative to improve silicon to a certain extent
The cyclical stability and first charge-discharge efficiency of pole.
One, the use of negative electrode binder, the present invention is using the more carboxyl structures of the tool such as the CMC of more carboxyls and sodium alginate
Binder, making carboxyl that complex reaction occur in this way makes silicon is even closer to be bonded together, and plays the role of inhibiting silicon expansion.
Two, it is difficult to form stable solid electrolyte interface in conventional lithium hexafluorophosphate electrolyte solution due to silicium cathode
(SEI) film constantly forms new SEI film in the silicon face exposed, exacerbates the corrosion of silicon with the destruction of electrode structure
And capacity attenuation.Therefore the present invention is sub- by adding carbonic acid in the electrolyte that lithium hexafluoro phosphate and di-oxalate lithium borate are solute
Vinyl acetate (abbreviation VC), succinic anhydride (SA) or fluorinated ethylene carbonate (FEC).SEI film component can occur after addition VC
Variation, generates the polymer of poly- alkyl lithium carbonates class, so that the flexibility of SEI film and adhesive force are stronger.And add succinic anhydride
(SA) or fluorinated ethylene carbonate (FEC) improves cycle performance well.The SEI film formed in conventional electrolysis liquid is main
Ingredient is inorganic lithium salt and a small amount of lithium alkylide, and flexibility is poor, and in contrast, the SEI film that VC base electrolyte is formed more can adapt to
Volume change of the silicon in charge and discharge process is without rupturing, to improve the cycle performance of battery.Silicium cathode is in mixing electricity
Solving in liquid has than chemical property better in single electrolyte.In addition, in electrolyte add succinic anhydride (SA) or
The cycle performance of silicium cathode also can be improved in fluorinated ethylene carbonate (FEC).
Three, another major reason for leading to silicium cathode capacity attenuation is that lithium hexafluoro phosphate decomposition generation is micro- in electrolyte
Amount HF causes to corrode to silicon.And the decomposition of lithium hexafluoro phosphate is primarily due to the presence of hydrone.Process is being made in the present invention
Middle to use high vacuum, the mode of high pure nitrogen circulation makes the content of water in battery core in 100PPm or less.
Four, in shape using the cylindrical structure that can bear high internal pressure, so that cathode is during expansion, shell has enough
Bearing capacity, prevent the expansion of cathode.
Preferably, the conductive agent in the positive plate, negative electrode tab is superp Li, carbon nanotube, graphene conductive agent
Middle one or several kinds, the binder on positive plate are Kynoar.
Preferably, the dispersing agent on the positive plate is sulfonated aromatic hydrocarbon polymer.
In addition, the dispersing agent in anode and cathode slurry is raw in practical application in the preparation process of existing conventional lithium battery
Dispersion effect is not especially desirable in production, causes intensity after final slurry curing inadequate, collection liquid surface positive active material and
Pole plate deformation, is also not easily controlled the weight of pole plate, increases the difficulty of coated plate while will cause the cost allowance of process.This hair
Bright selection sulfonated aromatic hydrocarbon polymer is mixed with and exists conducive to additive as dispersing agent, sulfonated aromatic hydrocarbon polymer and slurry other compositions
Dispersion effect in active material, the available better homogeneity of active material layer after solidification.Sulfonated aromatic hydrocarbon polymer is easy
It is produced in duplication, reduces production cost and step, can be promoted on a large scale.Sulfonated aromatic hydrocarbon polymer can be accelerated simultaneously
Battery charging conversion rate, shortens the charging time.Sulfonated aromatic hydrocarbon polymer can be reduced additive and active material incorporation time, allow
Pole plate generates better framework to resist convergent-divergent of the negative plate in charge and discharge process.
Preferably, the sulfonated aromatic hydrocarbon polymer is naphthalenesulfonateformaldehyde formaldehyde of the relative molecular mass in 10000-16000
Condensation product sodium salt, and the sulfonation degree of the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde is 70-100%.
As a molecular weight, the higher naphthalenesulfonateformaldehyde formaldehyde of sulfonation degree condensation product sodium salt can use dispersing agent, with go from
Solubility when sub- water mixes, which is easy for having reached 200g/L, is even up to 300g/L, soluble easily in water, and dispersion effect is good.
Preferably, the binder in the negative electrode tab is at least one of sodium carboxymethylcellulose, sodium alginate.
Preferably, the diaphragm is equipped with coating, the coating is polyvinylidene fluoride coating or ceramic coating.
Preferably, the collector of the positive plate is with a thickness of 6-12 μm, the collector of the negative electrode tab with a thickness of 6-
10μm。
Preferably, gram volume of the nickel cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, energy is close
Degree is in 683wh/kg or more；Silicone content is 42wt%, content of graphite 58wt%, silicon based composite material in the silicon based composite material
Gram volume under 4.2V-2.5V voltage is 650mAh/g or more, and energy density is in 2340wh/kg or more.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weigh following substance by weight percent: positive active material 95%-98%, conductive agent are
0.5%-2.0%, binder 0.5%-2.5%, dispersing agent 0.5%-1.0%；By the above-mentioned raw materials speed of revolution 10Hz-15Hz
It is premixed, adds N-Methyl pyrrolidone, be adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weigh following substance by weight percent: negative electrode active material 94%-97.7%, binder are
2.0%-4.0%, conductive agent 0.3%-2.0%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, are then added
Deionized water is adjusted to the slurry that viscosity is 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 490-510g/m2, will
Slurry obtained is coated on copper foil in step (3), coated face density 80-150g/m2；
(5) film-making: being 53 μm -98 μm thick by negative electrode tab pressure by positive plate pressure to be 144 μm -156 μm thick；Then by slitting
Machine fragment then by soldering polar ear on full-automatic pelleter, and is taped；
(6) it assembles: by automatic winding-machine by positive plate, the diaphragm of 6-16 μ m-thick, negative electrode tab, the membrane coil of 6-16 μ m-thick
It is coiled into the core that diameter is 17.0-17.5mm, internal diameter is then charged into as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative
It is toasted after the tab of pole, guarantees positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
The present invention passes through specific forming and capacity dividing technique, so that battery has preferable performance.
It is compared with the prior art, the beneficial effects of the present invention are: 18650 battery cores of the invention select specific positive and negative anodes material
Material cooperation, has very high energy density, and overcome many technological deficiencies during the preparation process, really is able to realization amount
It produces.
Detailed description of the invention
Fig. 1 is the performance test figure of the battery core of embodiment 5.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
A kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on the positive plate
Agent is superp Li, and binder is Kynoar.Dispersing agent on the positive plate is relative molecular mass in 10000-
16000, sulfonation degree is the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；Leading in the negative electrode tab
Electric agent is superp Li, and the binder in the negative electrode tab is sodium carboxymethylcellulose.
Wherein, the collector of the positive plate is with a thickness of 9 μm, the collector of the negative electrode tab with a thickness of 8 μm.The nickel
Gram volume of the cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, and energy density is in 683wh/kg or more；The silicon
Silicone content is 42wt%, content of graphite 58wt% in based composites, and the gram volume under silicon based composite material 4.2V-2.5V voltage is
650mAh/g or more, energy density is in 2340wh/kg or more.
The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride and carbon
The mixture of sour vinylene.The diaphragm is PP material, and the diaphragm is equipped with coating, and the coating is Kynoar painting
Layer.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weigh following substance by weight percent: positive active material 96.5%, conductive agent are
1.25%, binder 1.5%, dispersing agent 0.75%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, then plus
Enter N-Methyl pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weighing following substance: negative electrode active material 96% by weight percent, binder 3% is led
Electric agent is 1%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, deionized water are then added, being adjusted to viscosity is
The slurry of 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 500g/m2, by step
(3) slurry obtained is coated on copper foil in, coated face density 115g/m2；
(5) film-making: being 75 μm thick by negative electrode tab pressure by positive plate pressure to be 150 μm thick；Then by banding machine fragment, then
By soldering polar ear on full-automatic pelleter, and tape；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 11 μ m-thicks, negative electrode tab, 11 μ m-thicks membrane winding at
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes pole
It is toasted after ear, guarantees positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
Embodiment 2
A kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on the positive plate
Agent is carbon nanotube, and binder is Kynoar.Dispersing agent on the positive plate is relative molecular mass in 10000-
16000, sulfonation degree is the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；Leading in the negative electrode tab
Electric agent is carbon nanotube, and the binder in the negative electrode tab is sodium alginate.
Wherein, the collector of the positive plate is with a thickness of 6 μm, the collector of the negative electrode tab with a thickness of 6 μm.The nickel
Gram volume of the cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, and energy density is in 683wh/kg or more；The silicon
Silicone content is 42wt%, content of graphite 58wt% in based composites, and the gram volume under silicon based composite material 4.2V-2.5V voltage is
650mAh/g or more, energy density is in 2340wh/kg or more.
The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is fluoro ethylene carbonate
The mixture of ester and vinylene carbonate.The diaphragm is PE material.The diaphragm is equipped with coating, and the coating is that ceramics apply
Layer.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weighing following substance: positive active material 95% by weight percent, conductive agent 2.0%,
Binder is 2.5%, dispersing agent 0.5%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, add N- first
Base pyrrolidones is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weigh following substance: negative electrode active material 94% by weight percent, binder 4.0%,
Conductive agent is 2.0%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, deionized water is then added, is adjusted to glue
Degree is the slurry of 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 490g/m2, by step
(3) slurry obtained is coated on copper foil in, coated face density 80g/m2；
(5) film-making: being 53 μm thick by negative electrode tab pressure by positive plate pressure to be 144 μm thick；Then by banding machine fragment, then
By soldering polar ear on full-automatic pelleter, and tape；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 6 μ m-thicks, negative electrode tab, 6 μ m-thicks membrane winding Cheng Zhi
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes tab
After toasted, guarantee positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
Embodiment 3
A kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on the positive plate
Agent is graphene conductive agent, and binder is Kynoar.Dispersing agent on the positive plate is that relative molecular mass exists
The condensation product sodium salt of 10000-16000, the naphthalenesulfonateformaldehyde formaldehyde that sulfonation degree is 70-100%.
The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；Leading in the negative electrode tab
Electric agent is graphene conductive agent.Binder in the negative electrode tab is sodium carboxymethylcellulose and sodium alginate.
Wherein, the collector of the positive plate is with a thickness of 12 μm, the collector of the negative electrode tab with a thickness of 10 μm.It is described
Gram volume of the nickel cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, and energy density is in 683wh/kg or more；It is described
Silicone content is 42wt%, content of graphite 58wt%, the gram volume under silicon based composite material 4.2V-2.5V voltage in silicon based composite material
For 650mAh/g or more, energy density is in 2340wh/kg or more.
The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride, fluorine
For the mixture of ethylene carbonate and vinylene carbonate.The diaphragm is PP material.The diaphragm is equipped with coating, the painting
Layer is ceramic coating.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weighing following substance: positive active material 98% by weight percent, conductive agent 0.5%,
Binder is 0.5%, dispersing agent 1.0%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, add N- first
Base pyrrolidones is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weigh following substance by weight percent: negative electrode active material 97.7%, binder are
2.0%, conductive agent 0.3%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, deionized water is then added, adjusts
The slurry for being 2500 ± 1000Pa.s to viscosity；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 510g/m2, by step
(3) slurry obtained is coated on copper foil in, coated face density 150g/m2；
(5) film-making: being 98 μm thick by negative electrode tab pressure by positive plate pressure to be 156 μm thick；Then by banding machine fragment, then
By soldering polar ear on full-automatic pelleter, and tape；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 16 μ m-thicks, negative electrode tab, 16 μ m-thicks membrane winding at
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes pole
It is toasted after ear, guarantees positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
Embodiment 4
A kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on the positive plate
Agent is carbon nanotube, and binder is Kynoar.Dispersing agent on the positive plate is relative molecular mass in 10000-
16000, sulfonation degree is the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；It is viscous in the negative electrode tab
Tying agent is sodium carboxymethylcellulose and sodium alginate.
Wherein, the collector of the positive plate is with a thickness of 6-12 μm, the collector of the negative electrode tab with a thickness of 6-10 μm.
Gram volume of the nickel cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, and energy density is in 683wh/kg or more；
Silicone content is 42wt%, content of graphite 58wt%, gram under silicon based composite material 4.2V-2.5V voltage in the silicon based composite material
Capacity is 650mAh/g or more, and energy density is in 2340wh/kg or more.
The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride and carbon
The mixture of sour vinylene.The diaphragm is PP material.The diaphragm is equipped with coating, and the coating is ceramic coating.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weighing following substance: positive active material 96% by weight percent, and conductive agent 1% glues
Tying agent is 2%, dispersing agent 1%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, add N- methylpyrrole
Alkanone is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weighing following substance: negative electrode active material 95% by weight percent, binder 4% is led
Electric agent is 1%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, deionized water are then added, being adjusted to viscosity is
The slurry of 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 500g/m2, by step
(3) slurry obtained is coated on copper foil in, coated face density 100g/m2；
(5) film-making: being 75 μm thick by negative electrode tab pressure by positive plate pressure to be 150 μm thick；Then by banding machine fragment, then
By soldering polar ear on full-automatic pelleter, and tape；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 8 μ m-thicks, negative electrode tab, 8 μ m-thicks membrane winding Cheng Zhi
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes tab
After toasted, guarantee positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
Embodiment 5
A kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte.
The collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on the positive plate
Agent is carbon nanotube and graphene conductive agent composition, and binder is Kynoar.Dispersing agent on the positive plate is phase
To molecular mass in 10000-16000, the condensation product sodium salt for the naphthalenesulfonateformaldehyde formaldehyde that sulfonation degree is 70-100%.
The collector of the negative electrode tab is copper foil, and negative electrode active material is silicon based composite material；Leading on the positive plate
Electric agent is carbon nanotube and graphene conductive agent composition.Binder in the negative electrode tab is sodium carboxymethylcellulose and seaweed
Sour sodium.
Wherein, the collector of the positive plate is with a thickness of 9 μm, the collector of the negative electrode tab with a thickness of 8 μm.
Gram volume of the nickel cobalt lithium aluminate under 4.2V-2.5V voltage is 190mAh/g or more, and energy density exists
683wh/kg or more；The silicon based composite material uses Shenzhen City Beiterui New Energy Materials Co., Ltd model s650
The cathode of model, the gram volume under silicon based composite material 4.2V-2.5V voltage is 650mAh/g or more, and energy density exists
2340wh/kg or more.
The solute of the electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is fluoro ethylene carbonate
The mixture of ester and vinylene carbonate.The diaphragm is PP material.The diaphragm is equipped with coating, and the coating is that ceramics apply
Layer.
A kind of preparation method of 18650 battery cores of above-mentioned high-energy density, comprising the following steps:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: weighing following substance: positive active material 98% by weight percent, conductive agent 0.5%,
Binder is 0.5%, dispersing agent 1.0%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, add N- first
Base pyrrolidones is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weighing following substance: negative electrode active material 96% by weight percent, binder 2% is led
Electric agent is 2%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, deionized water are then added, being adjusted to viscosity is
The slurry of 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 490-510g/m2, will
Slurry obtained is coated on copper foil in step (3), coated face density 80-150g/m2；
(5) film-making: being 98 μm thick by negative electrode tab pressure by positive plate pressure to be 150 μm thick；Then by banding machine fragment, then
By soldering polar ear on full-automatic pelleter, and tape；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 12 μ m-thicks, negative electrode tab, 12 μ m-thicks membrane winding at
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes pole
It is toasted after ear, guarantees positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: in the glove box that humidity is less than -50 DEG C of dew point, 5.0 ± 0.5g electrolyte is injected, is vacuumized quiet
It sets after liquid to be electrolysed dries up and is sealed through row, be highly 18.0 ± 0.5mm after sealing.
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 0.6C electric current charging 80
Minute, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
Cycle life test is carried out to 18650 battery cores made from embodiment 5, test results are shown in figure 1.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (4)
1. a kind of 18650 battery cores of high-energy density, including shell, positive plate, negative electrode tab, diaphragm and electrolyte；Its feature exists
In: the collector of the positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of the negative electrode tab is copper
Foil, negative electrode active material are silicon based composite material；The diaphragm is PP or PE material；The solute of the electrolyte is hexafluorophosphoric acid
Lithium and di-oxalate lithium borate, the solvent of electrolyte are the mixture of succinic anhydride and vinylene carbonate；
Dispersing agent on the positive plate is condensation product sodium of the relative molecular mass in the naphthalenesulfonateformaldehyde formaldehyde of 10000-16000
Salt, and the sulfonation degree of the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde is 70-100%；Binder in the negative electrode tab is alginic acid
Sodium；The diaphragm is equipped with coating, and the coating is polyvinylidene fluoride coating or ceramic coating；
The preparation methods of 18650 battery cores of the high-energy density the following steps are included:
(1) material prepares: preparing positive active material and conductive agent and carries out powder drying；
(2) anode homogenate: following substance: positive active material 95%-98%, conductive agent 0.5%- are weighed by weight percent
2.0%, binder 0.5%-2.5%, dispersing agent 0.5%-1.0%；Above-mentioned raw materials are carried out with the speed of revolution 10Hz-15Hz
Premix, adds N-Methyl pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) cathode is homogenized: weigh following substance by weight percent: negative electrode active material 94%-97.7%, binder are
2.0%-4.0%, conductive agent 0.3%-2.0%；Above-mentioned raw materials are premixed with the speed of revolution 10Hz-15Hz, are then added
Deionized water is adjusted to the slurry that viscosity is 2500 ± 1000Pa.s；
(4) it is coated with: slurry obtained in step (2) is coated on aluminium foil, coating surface density is 490-510g/m2, by step
(3) slurry obtained is coated on copper foil in, coated face density 80-150g/m2；
(5) film-making: being 53 μm -98 μm thick by negative electrode tab pressure by positive plate pressure to be 144 μm -156 μm thick；Then by banding machine point
Piece then by full-automatic pelleter soldering polar ear, and is taped；
(6) assemble: by automatic winding-machine by positive plate, the diaphragm of 6-16 μ m-thick, negative electrode tab, 6-16 μ m-thick membrane winding at
Diameter is the core of 17.0-17.5mm, is then charged into internal diameter as 17.8mm, in the steel shell of a height of 18.2mm, welds positive and negative anodes pole
It is toasted after ear, guarantees positive water content in 100ppm hereinafter, cathode can carry out fluid injection after 300ppm or less；
(7) fluid injection: being to inject 5.0 ± 0.5g electrolyte in glove box less than -50 DEG C of dew point in humidity, vacuumize standing to
It is sealed after electrolyte dry-out, is highly 18.0 ± 0.5mm after sealing；
(8) forming and capacity dividing: after 45 DEG C stand 48 hours, with 0.2C electric current charging 10min, then with 80 points of 0.6C electric current charging
Clock, with 0.6C constant current constant voltage to 4.35V after standing 36 hours, then with 0.6C electric current constant-current discharge to 2.5V, recording capacity.
2. 18650 battery cores of high-energy density as described in claim 1, which is characterized in that on the positive plate, negative electrode tab
Conductive agent is superp Li, carbon nanotube, one or several kinds of in graphene conductive agent, and the binder on positive plate is poly- inclined
Vinyl fluoride.
3. 18650 battery cores of high-energy density as described in claim 1, which is characterized in that the collector of the positive plate is thick
Degree be 6-12 μm, the collector of the negative electrode tab with a thickness of 6-10 μm.
4. a kind of 18650 battery cores of high-energy density as described in claim 1, which is characterized in that the nickel cobalt lithium aluminate exists
Gram volume under 4.2V-2.5V voltage is 190mAh/g or more, and energy density is in 683wh/kg or more；The silicon based composite material
Middle silicone content is 42wt%, content of graphite 58wt%, the gram volume under silicon based composite material 4.2V-2.5V voltage be 650mAh/g with
On, energy density is in 2340wh/kg or more.
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| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
| CN104638234A (en) * | 2015-01-04 | 2015-05-20 | 深圳市贝特瑞新能源材料股份有限公司 | Negative active substance, negative pole piece and preparation method thereof as well as lithium ion battery |
| JP2015144108A (en) * | 2013-12-27 | 2015-08-06 | 旭硝子株式会社 | Surface-modified lithium-containing complex oxide for lithium ion secondary battery positive electrode |
| EP3179550A1 (en) * | 2015-12-08 | 2017-06-14 | Commissariat À L'Énergie Atomique Et Aux Énergies Alternatives | Electrochemical cell for lithium battery comprising an electrode made of a silicon-graphite composite material and a specific electrolyte |
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| CN1891668A (en) * | 2005-07-08 | 2007-01-10 | 中国科学院物理研究所 | Carbon-silicon composite material with spherical nucleocapsid, and its preparing method and use |
| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
| JP2015144108A (en) * | 2013-12-27 | 2015-08-06 | 旭硝子株式会社 | Surface-modified lithium-containing complex oxide for lithium ion secondary battery positive electrode |
| CN104638234A (en) * | 2015-01-04 | 2015-05-20 | 深圳市贝特瑞新能源材料股份有限公司 | Negative active substance, negative pole piece and preparation method thereof as well as lithium ion battery |
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