CN106257721A - A kind of 18650 battery cores of high-energy-density and preparation method thereof - Google Patents

A kind of 18650 battery cores of high-energy-density and preparation method thereof Download PDF

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CN106257721A
CN106257721A CN201610750599.XA CN201610750599A CN106257721A CN 106257721 A CN106257721 A CN 106257721A CN 201610750599 A CN201610750599 A CN 201610750599A CN 106257721 A CN106257721 A CN 106257721A
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energy
electrolyte
negative
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CN106257721B (en
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常福荣
任宁
常林荣
李洪涛
孙延先
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Zhejiang Chaowei Chuangyuan Industrial Co Ltd
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Zhejiang Chaowei Chuangyuan Industrial Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
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    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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 nickle cobalt lithium manganate 811;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

A kind of 18650 battery cores of high-energy-density and preparation method thereof
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 nickle cobalt lithium manganate 811;The afflux of described negative plate Body 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 six Lithium fluophosphate and di-oxalate lithium borate, the solvent of electrolyte is at least one in succinic anhydride, fluorinated ethylene carbonate and carbon The mixture of acid vinylene.
The present invention select nickle cobalt lithium manganate 811 and silicon based composite material respectively as both positive and negative polarity active substance, with above-mentioned After barrier film, electrolyte coordinate, there is higher energy density.But, silicon-based anode can occur huge in charge and discharge process Change in volume, causes capacity attenuation quickly.So not having producer to use in batches up to now, this invention takes multiple arranging Execute the volumetric expansion inhibiting silicon materials, and improve the electrical contact between silicon grain, thus improve silicon to a certain extent The cyclical stability of negative 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, the described nickle cobalt lithium manganate 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, energy Metric density is at more than 694wh/kg;In described silicon based composite material, silicone content is 42wt%, content of graphite 58wt%, silica-based composite wood Gram volume under material 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.
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 nickle cobalt lithium manganate 811.Leading on described positive plate Electricity 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 The cobalt manganic acid lithium 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, and energy density is at more than 694wh/kg;Institute Stating silicone content in silicon based composite material is 42wt%, content of graphite 58wt%, gram appearance under silicon based composite material 4.2V-2.5V voltage Amount 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, 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 nickle cobalt lithium manganate 811.Leading on described positive plate Electricity 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 The cobalt manganic acid lithium 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, and energy density is at more than 694wh/kg;Institute Stating silicone content in silicon based composite material is 42wt%, content of graphite 58wt%, gram appearance under silicon based composite material 4.2V-2.5V voltage Amount 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 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 nickle cobalt lithium manganate 811.Leading on described positive plate Electricity 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 The nickle cobalt lithium manganate 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, and energy density is at more than 694wh/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, 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 nickle cobalt lithium manganate 811.Leading on described positive plate Electricity 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. The described nickle cobalt lithium manganate 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, energy density 694wh/kg with On;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 volume be 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.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 nickle cobalt lithium manganate 811.Leading on described positive plate Electricity agent is CNT and graphene conductive agent composition, and binding agent is Kynoar.Dispersant on described positive plate is Relative molecular mass is 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.
The described nickle cobalt lithium manganate 811 gram volume under 4.2V-2.5V voltage is more than 200mAh/g, and energy density exists More than 694wh/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.
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 nickle cobalt lithium manganate 811;The collector of described negative plate is 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 phosphorus Acid lithium and di-oxalate lithium borate, the solvent of electrolyte is that at least one in succinic anhydride, fluorinated ethylene carbonate is sub-with carbonic acid The mixture of vinyl acetate.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 1, it is characterised in that described positive plate, negative plate On conductive agent be superp Li, CNT, in graphene conductive agent one or several, the binding agent on positive plate is Kynoar.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 2, it is characterised in that dividing on described positive plate Powder is sulfonated aromatic hydrocarbon polymer.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 3, it is characterised in that described sulfonated aromatic hydrocarbon is polymerized Thing is the relative molecular mass condensation product sodium salt at the naphthalenesulfonateformaldehyde formaldehyde of 10000-16000, and the condensation of naphthalenesulfonateformaldehyde formaldehyde is produced The sulfonation degree of thing sodium salt is 70-100%.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 1, it is characterised in that gluing on described negative plate Knot agent is at least one in sodium carboxymethyl cellulose, sodium alginate.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 1, it is characterised in that described barrier film is provided with painting Layer, described coating is polyvinylidene fluoride coating or ceramic coating.
18650 battery cores of a kind of high-energy-density the most as claimed in claim 1, it is characterised in that the afflux of described positive plate Body thickness 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 nickle cobalt lithium manganate 811 Gram volume under 4.2V-2.5V voltage is more than 200mAh/g, and energy density is at more than 694wh/kg;Described silica-based composite wood In material, silicone content is 42wt%, content of graphite 58wt%, and the gram volume under silicon based composite material 4.2V-2.5V voltage is 650mAh/g Above, energy density is at more than 2340wh/kg.
9. the preparation method of 18650 battery cores of a kind of high-energy-density as described in claim 1-8 is arbitrary, it is characterised in that Comprise 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 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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CN108428930A (en) * 2018-04-09 2018-08-21 惠州市赛能电池有限公司 A kind of method for making electric core of the negative plate containing silicon substrate
CN109103448A (en) * 2018-07-13 2018-12-28 金川集团股份有限公司 A kind of high capacity cylinder flexible packing lithium ion battery and its manufacturing method
CN115188922A (en) * 2022-06-24 2022-10-14 江苏正力新能电池技术有限公司 Silicon-based negative pole piece, secondary battery containing same and electricity utilization device

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CN104900916A (en) * 2015-06-26 2015-09-09 广州天赐高新材料股份有限公司 Electrolyte solution for high-capacity lithium-ion battery, preparation method and lithium-ion battery

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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
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