CN106299460A - 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
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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
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Abstract
The present invention relates to field of batteries, disclose 18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Described barrier film is PP or PE material；The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is the mixture of at least one in succinic anhydride, fluorinated ethylene carbonate and vinylene carbonate.18650 battery cores of the present invention select specific positive and negative pole material to coordinate, and have the highest energy density, and overcome many technological deficiencies in preparation process, really are able to realize volume production.
Description
Technical field
The present invention relates to field of batteries, 18650 battery cores particularly relating to a kind of high-energy-density and preparation method thereof.
Background technology
18650 is the founder of lithium ion battery, and Sony Corporation of Japan is then for cost-effective and that fix a kind of standard
Property lithium ion battery model, wherein 18 represent a diameter of 18mm, 65 represent a length of 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.
Now along with pure electric automobile flourish, the material of existing 18650 batteries and system collocation can not
The demand to energy density of electric automobile can not be met, battery itself must be improved for improving the course continuation mileage of electric automobile
Energy density, therefore needs badly and develops a 18650 batteries being applicable to electric automobile power battery.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides 18650 battery core and preparation sides thereof of a kind of high-energy-density
Method.18650 battery cores of the present invention select specific positive and negative pole material to coordinate, and have the highest energy density, and are preparing
Journey overcomes many technological deficiencies, really is able to realize volume production.
The concrete technical scheme of the present invention is: 18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative pole
Sheet, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of described negative plate
For Copper Foil, negative electrode active material is silicon based composite material；Described barrier film is PP or PE material；The solute of described electrolyte is hexafluoro
Lithium phosphate and di-oxalate lithium borate, the solvent of electrolyte is at least one in succinic anhydride, fluorinated ethylene carbonate and carbonic acid
The mixture of vinylene.
The present invention select nickel cobalt lithium aluminate and silicon based composite material respectively as both positive and negative polarity active substance, with above-mentioned every
After film, electrolyte coordinate, there is higher energy density.But, silicon-based anode can occur huge body in charge and discharge process
Long-pending change, causes capacity attenuation quickly.So not having producer to use in batches up to now, this invention takes many kinds of measures
Inhibit the volumetric expansion of silicon materials, and improve the electrical contact between silicon grain, thus improve silicon to a certain extent and bear
The cyclical stability of pole and first charge-discharge efficiency.
One, the use of negative electrode binder, the present invention uses CMC and the sodium alginate of many carboxyls etc. to have many carboxyl structure
Binding agent, so makes carboxyl generation complex reaction make silicon be bonded together more closely, plays the effect that suppression silicon expands.
Two, it is difficult to form stable solid electrolyte interface in conventional lithium hexafluorophosphate electrolyte solution due to silicium cathode
(SEI) film, along with the destruction of electrode structure, constantly forms new SEI film at the silicon face exposed, exacerbates the corrosion of silicon
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 (is called for short VC), succinic anhydride (SA) or fluorinated ethylene carbonate (FEC).After adding VC, SEI film component can occur
Change, generates the polymer of poly-alkyl lithium carbonates class so that pliability and the adhesive force of SEI film are higher.And add succinic anhydride
Or fluorinated ethylene carbonate (FEC) well improves cycle performance (SA).The SEI film formed in conventional electrolysis liquid is main
Composition is inorganic lithium salt and a small amount of lithium alkylide, and pliability is poor, and by contrast, the SEI film that VC base electrolyte is formed more can adapt to
Silicon change in volume in charge and discharge process and do not rupture, thus improve the cycle performance of battery.Silicium cathode is at mixing electricity
Solve in liquid and there is the more preferable chemical property than in single electrolyte..Additionally, in electrolyte add succinic anhydride (SA) or
Fluorinated ethylene carbonate (FEC) also can improve the cycle performance of silicium cathode.
Three, the another one major reason causing silicium cathode capacity attenuation is that in electrolyte, lithium hexafluoro phosphate decomposition produces micro-
Silicon is caused corrosion by amount HF.And the decomposition of lithium hexafluoro phosphate is primarily due to the existence of hydrone.The present invention is making process
Middle employing fine vacuum, the mode of high pure nitrogen circulation makes in battery core the content of water at below 100PPm.
Four, the cylindrical structure of high internal pressure can be born in profile employing so that negative pole is when expanding, and shell has enough
Bearing capacity, stop negative pole expansion.
As preferably, the conductive agent on described positive plate, negative plate is superp Li, CNT, graphene conductive agent
In one or several, the binding agent on positive plate is Kynoar.
As preferably, the dispersant on described positive plate is sulfonated aromatic hydrocarbon polymer.
Additionally, in the preparation process of existing conventional lithium battery, the dispersant in anode and cathode slurry is raw in reality application
In product, dispersion effect is not especially desirable, causes insufficient strength after final slurry curing, collection liquid surface positive active material and
Pole plate deforms, and is also not easily controlled the weight of pole plate, and the difficulty increasing coated plate can cause the cost allowance of process simultaneously.This
Bright selection sulfonated aromatic hydrocarbon polymer is mixed with beneficially additive as dispersant, sulfonated aromatic hydrocarbon polymer and other compositions of slurry and exists
Dispersion effect in active substance, the active material layer after solidification can obtain more preferable homogeneity.Sulfonated aromatic hydrocarbon polymer is easy
Produce in replicating, reduce production cost and step, can promote on a large scale.Sulfonated aromatic hydrocarbon polymer can be accelerated simultaneously
Battery charging switching rate, shortens the charging interval.Sulfonated aromatic hydrocarbon polymer can reduce additive and active substance incorporation time, allows
Pole plate produces more preferable framework to resist negative plate convergent-divergent in charge and discharge process.
As preferably, described sulfonated aromatic hydrocarbon polymer is the relative molecular mass naphthalenesulfonateformaldehyde formaldehyde at 10000-16000
Condensation product sodium salt, and the sulfonation degree of the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde is 70-100%.
Condensation product sodium salt as a molecular weight, naphthalenesulfonateformaldehyde formaldehyde that sulfonation degree is higher can use dispersant, with go from
The dissolubility during mixing of sub-water is easy for having reached 200g/L and is even up to 300g/L, soluble in water, and dispersion effect is good.
As preferably, the binding agent on described negative plate is at least one in sodium carboxymethyl cellulose, sodium alginate.
As preferably, described barrier film is provided with coating, and described coating is polyvinylidene fluoride coating or ceramic coating.
As preferably, the collector thickness of described positive plate is 6-12 μm, and the thickness of the collector of described negative plate is 6-
10μm。
As preferably, described nickel cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy is close
Degree is at more than 683wh/kg；In described silicon based composite material, silicone content is 42wt%, content of graphite 58wt%, silicon based composite material
Gram volume under 4.2V-2.5V voltage is more than 650mAh/g, and energy density is at more than 2340wh/kg.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 95%-98%, conductive agent is 0.5%-
2.0%, binding agent is 0.5%-2.5%, and dispersant is 0.5%-1.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is carried out
Premix, adds N-Methyl pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 94%-97.7%, binding agent is
2.0%-4.0%, conductive agent is 0.3%-2.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, is subsequently adding
Deionized water, is adjusted to the slurry that viscosity is 2500 ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 490-510g/m2, by step
(3) slurry prepared in is coated on Copper Foil, and coated face density is 80-150g/m2；
(5) film-making: being pressed by positive plate is thick 144 μm-156 μm, is thick 53 μm-98 μm by negative plate pressure；Then divided by banding machine
Sheet, then by soldering polar ear on full-automatic pelleter, and tapes；
(6) assembling: positive plate, the barrier film of 6-16 μ m-thick, negative plate, the membrane coil of 6-16 μ m-thick are coiled into by automatic winding-machine
The core of a diameter of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, in the box hat of a height of 18.2mm, welds both positive and negative polarity pole
Toast after ear, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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 is through specific forming and capacity dividing technique so that battery has preferable performance.
It is compared with the prior art, the invention has the beneficial effects as follows: 18650 battery cores of the present invention select specific both positive and negative polarity material
Material coordinates, and has the highest energy density, and overcomes many technological deficiencies in preparation process, really is able to realization amount
Produce.
Accompanying drawing explanation
Fig. 1 is the performance test figure of the battery core of embodiment 5.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on described positive plate
Agent is superp Li, and binding agent is Kynoar.Dispersant on described positive plate is that relative molecular mass is at 10000-
16000, sulfonation degree is the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Leading on described negative plate
Electricity agent is superp Li, and the binding agent on described negative plate is sodium carboxymethyl cellulose.
Wherein, the collector thickness of described positive plate is 9 μm, and the thickness of the collector of described negative plate is 8 μm.Described nickel
Cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density is at more than 683wh/kg；Described silicon
In based composites, silicone content is 42wt%, content of graphite 58wt%, and the gram volume under silicon based composite material 4.2V-2.5V voltage is
More than 650mAh/g, energy density is at more than 2340wh/kg.
The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride and carbon
The mixture of acid vinylene.Described barrier film is PP material, and described barrier film is provided with coating, and described coating is that Kynoar is coated with
Layer.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 96.5%, conductive agent is 1.25%, viscous
Knot agent is 1.5%, and dispersant is 0.75%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, adds N-methyl
Ketopyrrolidine, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 96%, binding agent is 3%, conductive agent
It is 1%；The speed of above-mentioned raw materials revolution 10Hz-15Hz being premixed, be subsequently adding deionized water, being adjusted to viscosity is 2500
The slurry of ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 500g/m2, by step (3)
In prepare slurry be coated on Copper Foil, coated face density is 115g/m2；
(5) film-making: being pressed by positive plate is thick 150 μm, is thick 75 μm by negative plate pressure；Then by banding machine burst, then by entirely
Automatically soldering polar ear on pelleter, and tape；
(6) assembling: positive plate, the barrier film of 11 μ m-thick, negative plate, the membrane coil of 11 μ m-thick are coiled into diameter by automatic winding-machine
For the core of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, in the box hat of a height of 18.2mm, after welding both positive and negative polarity lug
Toast, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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
18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on described positive plate
Agent is CNT, and binding agent is Kynoar.Dispersant on described positive plate is that relative molecular mass is at 10000-
16000, sulfonation degree is the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Leading on described negative plate
Electricity agent is CNT, and the binding agent on described negative plate is sodium alginate.
Wherein, the collector thickness of described positive plate is 6 μm, and the thickness of the collector of described negative plate is 6 μm.Described nickel
Cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density is at more than 683wh/kg；Described silicon
In based composites, silicone content is 42wt%, content of graphite 58wt%, and the gram volume under silicon based composite material 4.2V-2.5V voltage is
More than 650mAh/g, energy density is at more than 2340wh/kg.
The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is fluoro ethylene carbonate
Ester and the mixture of vinylene carbonate.Described barrier film is PE material.Described barrier film is provided with coating, and described coating is that pottery is coated with
Layer.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 95%, conductive agent is 2.0%, bonding
Agent is 2.5%, and dispersant is 0.5%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, adds N-methyl pyrrole
Pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 94%, binding agent is 4.0%, conduction
Agent is 2.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz being premixed, be subsequently adding deionized water, being adjusted to viscosity is
The slurry of 2500 ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 490g/m2, by step (3)
In prepare slurry be coated on Copper Foil, coated face density is 80g/m2；
(5) film-making: being pressed by positive plate is thick 144 μm, is thick 53 μm by negative plate pressure；Then by banding machine burst, then by entirely
Automatically soldering polar ear on pelleter, and tape；
(6) assembling: positive plate, the barrier film of 6 μ m-thick, negative plate, the membrane coil of 6 μ m-thick are coiled into a diameter of by automatic winding-machine
The core of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, and in the box hat of a height of 18.2mm, welding both positive and negative polarity lug is laggard
Row baking, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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
18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on described positive plate
Agent is graphene conductive agent, and binding agent is Kynoar.Dispersant on described positive plate is that relative molecular mass exists
10000-16000, sulfonation degree are the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Leading on described negative plate
Electricity agent is graphene conductive agent.Binding agent on described negative plate is sodium carboxymethyl cellulose and sodium alginate.
Wherein, the collector thickness of described positive plate is 12 μm, and the thickness of the collector of described negative plate is 10 μm.Described
Nickel cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density is at more than 683wh/kg；Described
In silicon based composite material, silicone content is 42wt%, content of graphite 58wt%, the gram volume under silicon based composite material 4.2V-2.5V voltage
For more than 650mAh/g, energy density is at more than 2340wh/kg.
The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride, fluorine
Mixture for ethylene carbonate Yu vinylene carbonate.Described barrier film is PP material.Described barrier film is provided with coating, described painting
Layer is ceramic coating.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 98%, conductive agent is 0.5%, bonding
Agent is 0.5%, and dispersant is 1.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, adds N-methyl pyrrole
Pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weigh following material by weight percent: negative electrode active material is 97.7%, and binding agent is 2.0%, leads
Electricity agent is 0.3%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, is subsequently adding deionized water, is adjusted to viscosity
It it is the slurry of 2500 ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 510g/m2, by step (3)
In prepare slurry be coated on Copper Foil, coated face density is 150g/m2；
(5) film-making: being pressed by positive plate is thick 156 μm, is thick 98 μm by negative plate pressure；Then by banding machine burst, then by entirely
Automatically soldering polar ear on pelleter, and tape；
(6) assembling: positive plate, the barrier film of 16 μ m-thick, negative plate, the membrane coil of 16 μ m-thick are coiled into diameter by automatic winding-machine
For the core of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, in the box hat of a height of 18.2mm, after welding both positive and negative polarity lug
Toast, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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
18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on described positive plate
Agent is CNT, and binding agent is Kynoar.Dispersant on described positive plate is that relative molecular mass is at 10000-
16000, sulfonation degree is the condensation product sodium salt of naphthalenesulfonateformaldehyde formaldehyde of 70-100%.
The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Gluing on described negative plate
Knot agent is sodium carboxymethyl cellulose and sodium alginate.
Wherein, the collector thickness of described positive plate is 6-12 μm, and the thickness of the collector of described negative plate is 6-10 μm.
Described nickel cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density is at more than 683wh/kg；
In described silicon based composite material, silicone content is 42wt%, content of graphite 58wt%, under silicon based composite material 4.2V-2.5V voltage gram
Capacity is more than 650mAh/g, and energy density is at more than 2340wh/kg.
The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is succinic anhydride and carbon
The mixture of acid vinylene.Described barrier film is PP material.Described barrier film is provided with coating, and described coating is ceramic coating.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 96%, conductive agent is 1%, binding agent
Being 2%, dispersant is 1%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, adds N-Methyl pyrrolidone,
It is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 95%, binding agent is 4%, conductive agent
It is 1%；The speed of above-mentioned raw materials revolution 10Hz-15Hz being premixed, be subsequently adding deionized water, being adjusted to viscosity is 2500
The slurry of ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 500g/m2, by step (3)
In prepare slurry be coated on Copper Foil, coated face density is 100g/m2；
(5) film-making: being pressed by positive plate is thick 150 μm, is thick 75 μm by negative plate pressure；Then by banding machine burst, then by entirely
Automatically soldering polar ear on pelleter, and tape；
(6) assembling: positive plate, the barrier film of 8 μ m-thick, negative plate, the membrane coil of 8 μ m-thick are coiled into a diameter of by automatic winding-machine
The core of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, and in the box hat of a height of 18.2mm, welding both positive and negative polarity lug is laggard
Row baking, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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
18650 battery cores of a kind of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte.
The collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate.Conduction on described positive plate
Agent is CNT and graphene conductive agent composition, and binding agent is Kynoar.Dispersant on described positive plate is phase
To molecular mass at the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde that 10000-16000, sulfonation degree are 70-100%.
The collector of described negative plate is Copper Foil, and negative electrode active material is silicon based composite material；Leading on described positive plate
Electricity agent is CNT and graphene conductive agent composition.Binding agent on described negative plate is sodium carboxymethyl cellulose and Sargassum
Acid sodium.
Wherein, the collector thickness of described positive plate is 9 μm, and the thickness of the collector of described negative plate is 8 μm.
Described nickel cobalt lithium aluminate gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density exists
More than 683wh/kg；Described silicon based composite material uses Shenzhen City Beiterui New Energy Materials Co., Ltd model to be s650
The negative pole of model, the gram volume under silicon based composite material 4.2V-2.5V voltage is more than 650mAh/g, and energy density exists
More than 2340wh/kg.
The solute of described electrolyte is lithium hexafluoro phosphate and di-oxalate lithium borate, and the solvent of electrolyte is fluoro ethylene carbonate
Ester and the mixture of vinylene carbonate.Described barrier film is PP material.Described barrier film is provided with coating, and described coating is that pottery is coated with
Layer.
The preparation method of 18650 battery cores of a kind of above-mentioned high-energy-density, comprises the following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 98%, conductive agent is 0.5%, bonding
Agent is 0.5%, and dispersant is 1.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, adds N-methyl pyrrole
Pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 96%, binding agent is 2%, conductive agent
It is 2%；The speed of above-mentioned raw materials revolution 10Hz-15Hz being premixed, be subsequently adding deionized water, being adjusted to viscosity is 2500
The slurry of ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 490-510g/m2, by step
(3) slurry prepared in is coated on Copper Foil, and coated face density is 80-150g/m2；
(5) film-making: being pressed by positive plate is thick 150 μm, is thick 98 μm by negative plate pressure；Then by banding machine burst, then by entirely
Automatically soldering polar ear on pelleter, and tape；
(6) assembling: positive plate, the barrier film of 12 μ m-thick, negative plate, the membrane coil of 12 μ m-thick are coiled into diameter by automatic winding-machine
For the core of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, in the box hat of a height of 18.2mm, after welding both positive and negative polarity lug
Toast, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm.
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, 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.
18650 battery cores preparing embodiment 5 are circulated life test, and test result is as shown in Figure 1.
Raw materials used, equipment in the present invention, unless otherwise noted, is the conventional raw material of this area, equipment；In the present invention
Method therefor, unless otherwise noted, is the conventional method of this area.
The above, be only presently preferred embodiments of the present invention, not impose any restrictions the present invention, every according to the present invention
Any simple modification, change and the equivalent transformation that above example is made by technical spirit, all still falls within the technology of the present invention side
The protection domain of case.
Claims (9)
1. 18650 battery cores of high-energy-density, including shell, positive plate, negative plate, barrier film and electrolyte；Its feature exists
In: the collector of described positive plate is aluminium foil, and positive active material is nickel cobalt lithium aluminate；The collector of described negative plate is copper
Paper tinsel, negative electrode active material is silicon based composite material；Described barrier film is PP or PE material；The solute of described electrolyte is hexafluorophosphoric acid
Lithium and di-oxalate lithium borate, the solvent of electrolyte is at least one in succinic anhydride, fluorinated ethylene carbonate and carbonic acid Asia second
The mixture of alkene ester.
2. 18650 battery cores of high-energy-density as claimed in claim 1, it is characterised in that on described positive plate, negative plate
Conductive agent is superp Li, CNT, in graphene conductive agent one or several, the binding agent on positive plate for poly-partially
Fluorothene.
3. 18650 battery cores of high-energy-density as claimed in claim 2, it is characterised in that the dispersant on described positive plate
For sulfonated aromatic hydrocarbon polymer.
4. 18650 battery cores of high-energy-density as claimed in claim 3, it is characterised in that described sulfonated aromatic hydrocarbon polymer is
Relative molecular mass is at the condensation product sodium salt of the naphthalenesulfonateformaldehyde formaldehyde of 10000-16000, and the condensation product sodium of naphthalenesulfonateformaldehyde formaldehyde
The sulfonation degree of salt is 70-100%.
5. 18650 battery cores of high-energy-density as claimed in claim 1, it is characterised in that the binding agent on described negative plate
For at least one in sodium carboxymethyl cellulose, sodium alginate.
6. 18650 battery cores of high-energy-density as claimed in claim 1, it is characterised in that described barrier film is provided with coating, institute
Stating coating is polyvinylidene fluoride coating or ceramic coating.
7. 18650 battery cores of high-energy-density as claimed in claim 1, it is characterised in that the collector of described positive plate is thick
Degree is 6-12 μm, and the thickness of the collector of described negative plate is 6-10 μm.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 1, it is characterised in that described nickel cobalt lithium aluminate exists
Gram volume under 4.2V-2.5V voltage is more than 190mAh/g, and energy density is at more than 683wh/kg；Described 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 at more than 2340wh/kg.
9. the preparation method of 18650 battery cores of the high-energy-density as described in claim 1-8 is arbitrary, it is characterised in that include
Following steps:
(1) material prepares: prepares positive active material and conductive agent and carries out powder and be dried；
(2) positive pole homogenate: weighing following material by weight percent: positive active material is 95%-98%, conductive agent is 0.5%-
2.0%, binding agent is 0.5%-2.5%, and dispersant is 0.5%-1.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is carried out
Premix, adds N-Methyl pyrrolidone, is adjusted to the slurry that viscosity is 7500 ± 1000Pa.s；
(3) negative pole homogenate: weighing following material by weight percent: negative electrode active material is 94%-97.7%, binding agent is
2.0%-4.0%, conductive agent is 0.3%-2.0%；The speed of above-mentioned raw materials revolution 10Hz-15Hz is premixed, is subsequently adding
Deionized water, is adjusted to the slurry that viscosity is 2500 ± 1000Pa.s；
(4) coating: being coated on aluminium foil by the slurry prepared in step (2), coated side density is 490-510g/m2, by step
(3) slurry prepared in is coated on Copper Foil, and coated face density is 80-150g/m2；
(5) film-making: being pressed by positive plate is thick 144 μm-156 μm, is thick 53 μm-98 μm by negative plate pressure；Then divided by banding machine
Sheet, then by soldering polar ear on full-automatic pelleter, and tapes；
(6) assembling: positive plate, the barrier film of 6-16 μ m-thick, negative plate, the membrane coil of 6-16 μ m-thick are coiled into by automatic winding-machine
The core of a diameter of 17.0-17.5mm, being then charged into internal diameter is 17.8mm, in the box hat of a height of 18.2mm, welds both positive and negative polarity pole
Toast after ear, it is ensured that positive pole water content is at below 100ppm, and negative pole can carry out fluid injection after below 300ppm；
(7) fluid injection: humidity be less than dew point-50 DEG C glove box in, inject 5.0 ± 0.5g electrolyte, evacuation stand treat
Through row sealing after electrolyte dry-out, after sealing, height is 18.0 ± 0.5mm；
(8) forming and capacity dividing: after standing 48 hours at 45 DEG C, with 0.2C electric current charging 10min, then charges 80 points with 0.6C electric current
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.
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| CN107219285A (en) * | 2017-04-19 | 2017-09-29 | 超威电源有限公司 | A kind of lead-acid accumulator test working electrode and preparation method thereof |
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