CN106450327A - Method for improving adhesive performance of lithium battery polyvinylidene fluoride by irradiation - Google Patents
Method for improving adhesive performance of lithium battery polyvinylidene fluoride by irradiation Download PDFInfo
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- CN106450327A CN106450327A CN201610895120.1A CN201610895120A CN106450327A CN 106450327 A CN106450327 A CN 106450327A CN 201610895120 A CN201610895120 A CN 201610895120A CN 106450327 A CN106450327 A CN 106450327A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
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- 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
A method for improving adhesive performance of lithium battery polyvinylidene fluoride by irradiation belongs to the technical field of lithium batteries. A lithium battery with polyvinylidene fluoride (PVDF) adhesive is prepared, the whole battery is placed under an electronic accelerator or on a radiation processing device of Dynamitron and is exposed to irradiation under the irradiation dosage of 20-200 kGy and irradiation dosage rate of 50-15000 Gy/s, PVDF is partially crosslinked, the adhesive performance of PVDF is changed, battery thickness bulking rate is decreased, capacity retention of the battery is increased, battery stability is improved, and the service life of the battery is prolonged.
Description
Technical field
The invention belongs to technical field of lithium batteries, it is related to the side that a kind of irradiation improves lithium battery Kynoar gluing performance
Method.
Background technology
The energy is the material base that the mankind depend on for existence and development.Fossil fuel (coal, oil, natural gas) is always the mankind
The main body of using energy source.Develop rapidly with social, fossil fuel non-renewable, reserves are limited and combustion process causes
Environmental pollution the problems such as gradually highlight.Converted by natural energies such as wind energy, solar energy, water power energy, geothermal energy, ocean energies
The electric power obtaining, because of stability and poor continuity it is impossible to large-scale application.Battery, especially secondary cell are as by discontinuously
Electric power store the energy storage medium that smoothly discharges again in application it is achieved that novel energy effectively utilizes.
Lithium ion battery is developed by lithium battery.Lithium battery is a kind of with lithium metal or lithium alloy for negative pole work
The general name of the electrochmical power source of property material, including lithium primary battery and lithium secondary battery.Lithium is all elements Plays electrode potential
The most negative (- 3.045V, vs.SHE), density minimum (0.53g cm-3), electrochemical equivalent highest (0.26g Ah-1) and theoretical specific volume
Amount highest (3861mAh g-1) metallic element.So, when with lithium metal for negative pole, battery has high operating voltage, height
Energy density and power density.Research to lithium battery starts from 20th century six the seventies, and current lithium ion battery is compared with it
Energy is high, power density is high, have extended cycle life, self discharge is little, cost performance ratio has become as current portable electric
The main selecting object of the rechargeable formula power supply of sub- product.Be not only applicable to the skinny devices such as mobile phone, computer, apply equally to
On electric automobile headed by tesla, for alleviating environmental pressure, the mixed of battery and machine power is competitively supported in countries in the world
Close electric automobile (HEV), such commercial automobile progressively increases.Lithium ion battery, its core component is generally by following components
Composition：Positive pole, negative pole, electrolyte, barrier film and auxiliary accessories.Wherein both positive and negative polarity is the core of lithium ion battery, is lithium
Ion provides embedded and abjection carrier.The lithium ion battery of commercialization on the market, usually soft bag lithium ionic cell.Electricity
Frequently with oleaginous system, its active material is cobalt acid lithium (LiCoO to the positive pole in pond2), binding agent is Kynoar (PVDF), molten
Agent is 1-METHYLPYRROLIDONE (NMP)；The negative active core-shell material of battery is native graphite, Delanium, MCMB
Or mixture (CMS).Can be generally divided into aqueous and oleaginous system, wherein water-based system adopts CMC/SBR (styrene-fourth two
Alkene rubber) as binding agent, there is the advantage of environmental protection, low cost, and oleaginous system generally adopts PVDF for bonding agent, solvent is
NMP, the advantage of oleaginous system is that the dynamic performance of battery and cryogenic property are more preferable.
Bonding agent, as the important component part of battery plus-negative plate material, in general charge and discharge process, at least plays
Several basic roles below：1) adhesion activity material (particularly powder)；2) active material is made to adhere to colelctor electrode；3) exist
Play preservation adhesion activity material (particularly powder) in charge and discharge process and so that active material is adhered to colelctor electrode；4) giving birth to
Form pulpous state, beneficial to coating etc. during product.Bonding agent as lithium battery, it is necessary to have following performance：1) good heat-resisting
Property, lithium ion needs strictly to control moisture in process of production, and pole plate will be completely dried and be heated under 200 degree；
2) solvent resistance, does not dissolve in the electrolytic solution, as few as possible expansion, otherwise can gradually lose bonding effect；3) electrochemistry
, to oxidisability positive pole and reproducibility negative pole chemically stable, there is not chemistry, electrochemical reaction in stability；4) there is comparison high
Electronic and ionic electric conductivity；5) consumption is few, cheap, and processability is good.
- CF is contained on PVDF strand2, dielectric constant is higher, is conducive to the dissociation of lithium salts, has mechanical property good, electric
Stable chemical performance, to the good stability of electrode the advantages of, this polymer has the stability of typical fluoropolymer simultaneously,
Interactive group on polymer chain can produce a unique polarity.This polarity can affect the solubility of polymer and lithium ion,
Interaction force between active position and metal collector.PVDF is for positive poles multiple in lithium battery, negative material ratio simultaneously
More stable, just react more than 200 degree with lithium, outside the safe handling scope of battery, excellent performance makes it become
For the major product in commercial battery.From 300,000～3,000,000, mainly there is French A Kema in manufacturer to PVDF molecular weight
(Arkema) PVDFHSV900, Belgian Su Wei (Solvay) 5130, Japanese Wu Yu chemistry KFl300, U.S. 3M, Shanghai three is liked
Rich PVDF FR921-2 etc..In positive pole, the batch mixing of negative pole film, bonding agent content used is to discharge capacity, high-rate discharge ability
All there is great impact with cycle life, internal resistance.When PVDF consumption is less, in the case of guaranteeing adhesive effect, electrode activity
Material utilization will be high, and initial discharge capacity is just high, but unfavorable to cycle performance of battery；PVDF consumption is very few, and negative pole exists
Soak in nipping process or through electrolyte and be easy to come off, positive pole is then larger due to proportion, slurry is easy to settle in coating process
Layering；When PVDF consumption is more, electrode active material utilization rate is low, and discharge capacity is low, and battery polarization internal resistance increases, discharge platform
Reduce, unfavorable to high-multiplying power discharge, but cyclical stability improves.Therefore positive pole PVDF content with the 1～5% of solid phase gross weight is
Preferably, negative pole PVDF content is advisable with the 1～7% of solid phase gross weight.In existing goods, because PVDF degree of crystallinity is high, meeting in NMP
Slowly swelling, bonding force is gradually lowered, and battery can be made to decay soon in cyclic process, and resistance increases soon, affects performance and electricity
Pond service life.Therefore, need badly and PVDF is modified, solve industry rigid demand.
Irradiation grafting modification is to be grafted some monomers or oligomer using irradiation in polymer surfaces, reaches change material
The purpose of energy.It is an important method of macromolecule material surface modification, because of its unique advantage, on multiple macromolecular materials all
There is preferable application.It is modified that irradiation grafting is also widely used in PVDF.For PVDF, no matter it is grafted onto main chain method (first
First synthesis has main polymer chain and the side chain of reactive functional groups, by the chemical reaction between two functional groups, by polymer
Side chain is incorporated on main polymer chain), or main chain Graft Method (synthesis has the main polymer chain at initiating activity center first,
Then cause second monomer to be polymerized by the activated centre on main chain), can well PVDF be modified, because
This researchers can give the more excellent performance of PVDF by different grafted chains.Research to irradiation grafting product finds, spoke
The polymer obtaining according to grafting is highly stable, and excellent performance is conducive to permanent effectiveness in the devices.
Battery material bonding agent needs heat-resisting, solvent resistant, stable, and other impurities therefore can not be had in use to ooze
Go out, be the most suitable from irradiation grafting method.Direct or indirect graft modification is carried out to PVDF thin film, overcomes its crystallization
Degree is high, expand after bonding force be deteriorated, aging the shortcomings of, improve its caking property in soft bag lithium ionic cell positive and negative pole material
Energy.Modified product is substantially to improve cohesive force and cohesive force by increasing interface wellability, thus reduce swellability so that
Cell thickness is stable, maintains energy density, improves service life.
The modification of Kynoar mainly has chemical graft and irradiation grafting, irradiation grafting and traditional chemical grafting method phase
Ratio has the characteristics that its own.1) graft reaction that irradiance method causes is more more than conventional method.For example with chemical method to solid
When state fiber carries out graft modification, it is hardly formed uniform initiation point on its surface, and utilizes ionizing radiation, particularly in energy
Height, irradiation under conditions of penetration power is strong, can extensively be formed uniformly free radical in whole solid fabric, be easy to graft reaction
Carry out.2) ionizing radiation can be by the non-selective absorption of material.In principle, irradiation grafting technology can apply to any pair of polymerization
The graft copolymerization of thing one monomer system.3) irradiation grafting is easier to carry out, and simple to operate, also may be used under room temperature or even low temperature
Complete.Meanwhile, reaction can be controlled by adjusting the methods such as dosage, close rate, monomer concentration, thus obtaining the grafting of needs
Speed, percent grafting and grafting concentration (surface or bulk graft).4) irradiation grafting reaction does not need extraneous introducing initiator, therefore
There is not initiator residual, can clean, safe graft copolymer, and ensure the purity of polymer.
PVDF, because of its distinctive physicochemical properties, has had multiple graft-modified polymers to be applied to the devices such as battery
In, but, existing document is concentrated mainly on modified PVDF membrane for directions such as proton exchange although present commercial batteries are wide
General PVDF is used as the bonding agent of positive electrode and negative material, but the work of radiation modification PVDF bonding agent yet there are no report
Road.Refer to the consumption of PVDF in the patent of a small amount of company, and mix the technique of masking with other powder it was also proposed that PVDF
The viscosity existing as bonding agent is inadequate, and the problems such as dilatancy, but also do not find particularly suitable process
[CN101412835-A,CN101136467-A,CN1277236-A].
In view of this, it is necessory to provide a kind of technical side that can improve PVDF adhesive performance in lithium ion battery
Case.
Content of the invention
The present invention provide a kind of by the radiation modification battery scheme of PVDF gluing performance, by simple irradiation, energy
The performance of modified adhesive, improves the performance of battery.
Concrete scheme is as follows：Comprise the following steps
(1) prepare lithium battery, battery structure is soft bag lithium ionic cell, and positive plate, barrier film and negative plate are rolled up in order
It is coiled into battery core, with aluminium profiles film by battery core closedtop and side seal, leave liquid injection port perfusion electrolyte, then through works such as chemical conversion, capacity
Sequence is obtained lithium ion battery；
Wherein positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on described plus plate current-collecting body, positive pole diaphragm bag
Include positive active material, bonding agent and conductive agent, positive electrode active materials are preferably LiMn2O4, cobalt acid lithium, nickle cobalt lithium manganate etc.
Plant or several mixtures；Bonding agent be preferably Kynoar (PVDF), polyvinyl alcohol bonding agent, polyurethane adhesive,
One of epoxy resin adhesive or several mixtures；Conductive agent is preferably conductive black, superconduction carbon black, electrically conductive graphite
With CNT one or more；
Battery cathode sheet includes negative current collector and is coated in the cathode membrane on described negative current collector surface, cathode membrane
Including material with carbon element, bonding agent and conductive agent；Material with carbon element be preferably native graphite, carbonaceous mesophase spherules, one kind of Delanium or
Several mixture of person；Bonding agent is PVDF, and conductive agent is preferably conductive black, superconduction carbon, acetylene black, Graphene, carbon fiber
One or more mixture.
(2) the radiation modification method of lithium ion battery, step (1) gained lithium ion battery is integrally placed to electronics and accelerates
Integrally carry out irradiation under device or on device under the bundle of dynamitron to lithium ion battery, adjust irradiation apparatus parameter, make
Obtaining irradiation dose is 20～200kGy, preferably 30～120kGy, and radiation dose rate is 50～15000Gy/s, preferably 2000
～10000Gy/s, carries out the radiation treatment of doses so that PVDF is partial cross-linked to lithium ion battery, thus changing its glue
Stickiness energy, and then improve stability test.Dosage is too low, crosslinked insufficient, insufficient strength, and gluing performance is difficult to improve, dosage
Too high, the degree of cross linking is too big, and not, gluing performance also can be deteriorated the pliability of PVDF, is unfavorable for the multiple circulation of battery.
The preparation of above-mentioned steps (1) lithium ion battery comprises the following steps：
Step one：The preparation of based lithium-ion battery positive plate, by positive active material, bonding agent and conductive agent according to certain
Mass ratio is blended in solvent such as 1-METHYLPYRROLIDONE (NMP), stirs, obtains anode sizing agent.The positive pole obtaining is starched
Material is coated on certain thickness plus plate current-collecting body as on aluminium foil, is dried, colds pressing, obtain compacted density in 1.4～1.6g/cm3
Pole piece, then through cut-parts, soldering polar ear, obtain positive plate；
Step 2：The preparation of anode plate for lithium ionic cell, by carbon element, bonding agent and conductive agent according to
Certain mass ratio is blended in solvent such as NMP, after mixing, obtains cathode size, is then coated on cathode size negative
On the collector of pole, such as Copper Foil, form cathode membrane after drying, process is colded pressing, article points, soldering polar ear obtains negative plate.
Step 3：The electrolyte of lithium ion battery, by methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate
Ester (EC), propene carbonate (PC) mix according to a certain percentage, add certain density lithium hexafluoro phosphate as solute, make
Become electrolyte.
Step 4：Barrier film, using polyethylene porous membrane, porous film thickness is 15～20 μm.
Step 5：The assembling of lithium battery, the positive plate obtaining, negative plate and barrier film is wound into battery core in order, uses aluminium
Type film, by battery core closedtop and side seal, leaves liquid injection port perfusion electrolyte, then lithium-ion electric is obtained through operations such as chemical conversion, capacity
Pond.
Preferably in positive pole diaphragm, the mass ratio of positive active material, bonding agent and conductive agent is 95:3:2；Bonding agent is preferred
For one of Kynoar (PVDF), polyvinyl alcohol bonding agent, polyurethane adhesive, epoxy resin adhesive or several
Mixture；Further preferably the bonding agent in positive pole diaphragm at least includes Kynoar (PVDF), and content is lived for positive pole
The 0.5%～6% of the gross weight of property material layer；It is further preferred that the content of positive pole bonding agent PVDF is positive active material
The 1%～5% of layer gross weight.
Preferably in cathode membrane, the mass ratio of material with carbon element, bonding agent and conductive agent is 96:2:2；Preferably in cathode membrane
Bonding agent at least includes Kynoar (PVDF), and content is the 0.05%～5% of the gross weight of negative electrode active material layer；Enter
Preferably, the content of negative pole bonding agent is the 0.5%～4% of negative electrode active material layer gross weight to one step.
With respect to prior art, the overall irradiation of battery, decrease procedure, using ground nanometer accelerator or electronics
Accelerator, safer than cobalt source accelerator, it is also easier to control device parameter, thus controlling the crosslinking degree of PVDF.This skill
Art scheme by improve PVDF the degree of cross linking so that in battery core PVDF adhesive there is more preferable gluing performance, be not likely to produce stripping
From, reduce swellability so that cell thickness is stable, favourable to the circulatory system of battery, maintain energy density, improve and use the longevity
Life.The key innovations of the present invention are, lithium battery anode piece, cathode pole piece preparation process is simple are it is not necessary to enter to PVDF
Row is heat-treated or is chemically treated to adjust its crystal formation or Film Morphology it is only necessary to directly put the lithium ion battery assembling
Carry out overall irradiation under dynamitron or electron accelerator.Modified technique is simply efficient, and exposure time is short, effect
Good.With respect to the cobalt source irradiation of early stage, production efficiency is higher, safer.Can raising PVDF rapidly and efficiently bear in lithium battery
Adhesive property in the pole piece of pole so that thickness swelling after circulation repeatedly for the battery substantially reduces, protect by the capacity improving battery
Holdup, substantially prolongs the service life of battery, thus the user satisfaction of consumer is greatly improved, and then improves such
The market position of battery.
Specific embodiment
With reference to embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1：
The preparation of based lithium-ion battery positive plate：
By positive active material cobalt acid lithium, nickle cobalt lithium manganate, conductive carbon, binding agent PVDF according to 70:25:3:2 quality
Ratio is blended in solvent NMP, stirs, and obtains anode sizing agent.The anode sizing agent obtaining is coated on 9 μm of aluminium foil, does
Dry, cold pressing, obtain compacted density in 1.5g/cm3Pole piece, then through cut-parts, soldering polar ear, obtain positive plate.
The preparation of anode plate for lithium ionic cell：
By negative electrode active material native graphite, conductive carbon, binding agent PVDF (whole melting temperatur is 160 degree) according to mass ratio
96:2:2 add in solvent NMP, after mixing, obtain cathode size, then cathode size is coated in the metal of 8 μ m-thick
The two sides of Copper Foil, is dried into the cathode pole piece with certain suppleness, and process is colded pressing, article points, and soldering polar ear obtains negative plate.
The preparation of the electrolyte of lithium ion battery：
By methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propene carbonate (PC) are according to 1:
1:0.5:0.5 mass ratio mixes, and adds lithium hexafluoro phosphate (LiPF6) as solute, make the concentration of lithium hexafluoro phosphate
For 1mol/L, make electrolyte.
Barrier film adopts polyethylene porous membrane, and porous film thickness is 16 μm.
The preparation of lithium battery：
Positive plate, negative plate and barrier film are wound into battery core in order, with aluminium profiles film by battery core closedtop and side seal, stay
Liquid injection port irrigates electrolyte, then lithium ion battery is obtained through operations such as chemical conversion, capacity.
The irradiation of lithium ion battery：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 5000Gy/s, carries out radiation treatment to lithium ion battery, irradiation dose is 40kGy, makes
Obtain PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Embodiment 2：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 5000Gy/s, carries out radiation treatment to lithium ion battery, irradiation dose is 70kGy, makes
Obtain PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 3：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 5000Gy/s, carries out radiation treatment to lithium ion battery, and irradiation dose is 100kGy,
Make PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 4：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 5000Gy/s, carries out radiation treatment to lithium ion battery, and irradiation dose is 130kGy,
Make PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 5：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 8000Gy/s, carries out radiation treatment to lithium ion battery, irradiation dose is 40kGy, makes
Obtain PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 6：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 8000Gy/s, carries out radiation treatment to lithium ion battery, irradiation dose is 70kGy, makes
Obtain PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 7：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 8000Gy/s, carries out radiation treatment to lithium ion battery, and irradiation dose is 100kGy,
Make PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 8：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under dynamitron, dolly loads, tiles in order.Optionally
That meter of accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, is filled under accelerator energy and accelerator bundle by adjusting
The gait of march put, so that close rate is 8000Gy/s, carries out radiation treatment to lithium ion battery, and irradiation dose is 130kGy,
Make PVDF partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 9：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under electron accelerator, dolly loads, tiles in order.From electronics
Accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator bundle
Gait of march so that close rate be 5000Gy/s, radiation treatment is carried out to lithium ion battery, irradiation dose be 40kGy so that
PVDF is partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 10：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under electron accelerator, dolly loads, tiles in order.From electronics
Accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator bundle
Gait of march so that close rate be 5000Gy/s, radiation treatment is carried out to lithium ion battery, irradiation dose be 70kGy so that
PVDF is partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 11：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under electron accelerator, dolly loads, tiles in order.From electronics
Accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator bundle
Gait of march so that close rate be 5000Gy/s, radiation treatment is carried out to lithium ion battery, irradiation dose be 100kGy so that
PVDF is partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Embodiment 12：
The irradiation of lithium ion battery as different from Example 1：
Lithium ion battery is placed on device under the bundle under electron accelerator, dolly loads, tiles in order.From electronics
Accelerator, accelerator energy is 5MeV, adjusts irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator bundle
Gait of march so that close rate be 5000Gy/s, radiation treatment is carried out to lithium ion battery, irradiation dose be 130kGy so that
PVDF is partial cross-linked.Afterwards lithium ion battery is taken out from dolly, test battery performance.
Remaining is with embodiment 1.
Comparative example 1：
Preparing of lithium battery is same as Example 1, and except for the difference that comparative example does not carry out radiation modification.Carry out lithium battery to calculate
Terminate.
For check test effect, the battery in all embodiments and comparative example adopts same series-produced lithium ion battery,
Battery in each embodiment and comparative example has 20 pieces, and carries out the test of battery respectively.Test data is as follows：
Split to using the method preparation of embodiment 1 to 12 and comparative example 1 and the lithium battery of radiation modification, adopt
The reverse stripping method of 180 degree carries out cohesive force test, 5 samples of every group of selection, tests every group of sample, averages and carry out bonding force
Comparison, acquired results are shown in Table one.
Table 1：The negative plate being obtained after splitting using the battery of the method preparation of embodiment 1 to 12 and comparative example 1 viscous
Relay test result.
As can be seen from Table 1, the bonding force of the negative plate prepared using the inventive method is apparently higher than using comparative example
The negative plate of method preparation, this shows that the method for the present invention can significantly improve the bonding force of negative plate.
In battery industry, PVDF can be slowly swelling in NMP, and bonding force is gradually lowered, and can make battery in cyclic process
Middle decay is fast, and resistance increases soon, affects performance and battery.Radiation modification is substantially by properly increasing PVDF
The degree of cross linking, thus increasing interface wellability to improve cohesive force and cohesive force, thus reduce swellability so that cell thickness is steady
Fixed, maintain energy density, improve service life.
Carry out following at 25 DEG C to using the method preparation of embodiment 1 to 12 and comparative example 1 and the lithium battery of radiation modification
Ring test, and respectively record 100 times circulation, 200 times circulation, 400 times circulation (rate of charge and discharge-rate are 0.5C) after
Battery thickness swelling, every group selection 5 samples, test every group of sample, average and carry out the comparison of thickness swelling,
Acquired results are shown in Table 2.
Table 2：Circulating battery expansion rate test result using the method preparation of embodiment 1 to 12 and comparative example 1
The result of table 2 shows, using the inventive method, irradiated after battery, the thickness after circulating battery is multiple is swollen
Swollen substantially diminish, to a certain extent also after explanation irradiation, the gluing performance of PVDF improves so that pole piece has higher bonding
So that the expansion bounce-back of negative plate reduces, the circulation that reduce further battery expands performance.Life-span after lithium ion battery circulation
It is obviously improved.
Carry out following under 45 degree to using the method preparation of embodiment 1 to 12 and comparative example 1 and the lithium battery of radiation modification
Ring test, and respectively record 100 times circulation, 200 times circulation, 400 times circulation after battery capability retention, every group choose 5
Individual sample, tests every group of sample, averages and carry out the comparison of thickness swelling, acquired results are shown in Table 3.
Table 3：Circulating battery plot ratio test result using the method preparation of embodiment 1 to 12 and comparative example 1
The result of table 3 shows, using the inventive method, irradiated after battery, the battery after circulating battery is multiple holds
Amount conservation rate is obviously improved, and shows PVDF adhesive after cross-linking radiation, and the stability of battery improves, and deformation rate is little,
Battery capacity conservation rate is high, and after lithium ion battery circulation, the life-span is obviously improved.
The announcement of book and guidance according to the above description, those skilled in the art in the invention can also be to above-mentioned experiment side
Case carries out suitable change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
In the claim and protection domain that some modifications and changes of invention should also be as fall into the present invention.Although additionally, this specification
In employ some specific terms, but these terms are merely for convenience of description, do not constitute any restriction to the present invention.
Claims (7)
1. a kind of irradiation improves the method for lithium battery Kynoar gluing performance it is characterised in that comprising the following steps：
(1) prepare lithium battery, battery structure is soft bag lithium ionic cell, and positive plate, barrier film and negative plate are wound in order
Battery core, with aluminium profiles film by battery core closedtop and side seal, leaves liquid injection port perfusion electrolyte, then is obtained through chemical conversion, capacity operation
Lithium ion battery；
Wherein positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on described plus plate current-collecting body, and positive pole diaphragm is just included
Pole active material, bonding agent and conductive agent, positive electrode active materials are that LiMn2O4, cobalt acid lithium, nickle cobalt lithium manganate etc. are a kind of or several
The mixture planted；Bonding agent is preferably Kynoar (PVDF), polyvinyl alcohol bonding agent, polyurethane adhesive, epoxy resin
One of bonding agent or several mixtures；Conductive agent is conductive black, superconduction carbon black, electrically conductive graphite and CNT
One or more；
Battery cathode sheet includes negative current collector and is coated in the cathode membrane on described negative current collector surface, and cathode membrane includes
Material with carbon element, bonding agent and conductive agent；Material with carbon element is preferably native graphite, carbonaceous mesophase spherules, one kind of Delanium or several
The mixture planted；Bonding agent be PVDF, conductive agent be conductive black, superconduction carbon, acetylene black, Graphene, one kind of carbon fiber or
The multiple mixture of person；
(2) the radiation modification method of lithium ion battery, step (1) gained lithium ion battery is integrally placed under electron accelerator
Or irradiation integrally carried out to lithium ion battery on device under the bundle of dynamitron, adjusts irradiation apparatus parameter so that spoke
It is 20～200kGy according to dosage, radiation dose rate is 50～15000Gy/s, and lithium ion battery is carried out at the irradiation of doses
Reason, so that PVDF is partial cross-linked, thus changing its gluing performance, and then improves stability test.
2. improve the method for lithium battery Kynoar gluing performance it is characterised in that spoke according to a kind of irradiation of claim 1
It is 30～120kGy according to dosage, radiation dose rate is 2000～10000Gy/s.
3. improve the method for lithium battery Kynoar gluing performance it is characterised in that walking according to a kind of irradiation of claim 1
Suddenly the preparation of (1) lithium ion battery comprises the following steps：
Step one：The preparation of based lithium-ion battery positive plate, by positive active material, bonding agent and conductive agent according to certain quality
Than mixing more in a solvent, stir, obtain anode sizing agent.The anode sizing agent obtaining is coated on certain thickness anode collection
On body, it is dried, colds pressing, obtain compacted density in 1.4～1.6g/cm3Pole piece, then through cut-parts, soldering polar ear, obtain positive pole
Piece；
Step 2：The preparation of anode plate for lithium ionic cell, by carbon element, bonding agent and conductive agent according to certain
Mass ratio mix in a solvent, after mixing, obtain cathode size, then cathode size be coated on negative current collector
On, such as Copper Foil, form cathode membrane after drying, process is colded pressing, article points, soldering polar ear obtains negative plate；
Step 3：The electrolyte of lithium ion battery, by methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate
(EC), propene carbonate (PC) mixes according to a certain percentage, adds certain density lithium hexafluoro phosphate as solute, makes
Electrolyte；
Step 4：Barrier film, using polyethylene porous membrane, porous film thickness is 15～20 μm.
Step 5：The assembling of lithium battery, the positive plate obtaining, negative plate and barrier film are wound into battery core in order, thin with aluminium profiles
Film, by battery core closedtop and side seal, leaves liquid injection port perfusion electrolyte, then lithium ion battery is obtained through operations such as chemical conversion, capacity.
4. improve the method for lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1 it is characterised in that excellent
Positive active material in positive pole diaphragm, bonding agent, the mass ratio of conductive agent is selected to be 95:3:2.
5. improve the method for lithium battery Kynoar gluing performance it is characterised in that just according to a kind of irradiation of claim 1
Bonding agent in the diaphragm of pole at least includes Kynoar (PVDF), and content is the gross weight of positive electrode active material layer
0.5%～6%；It is further preferred that the content of positive pole bonding agent PVDF is the 1%～5% of positive electrode active material layer gross weight.
6. improve the method for lithium battery Kynoar gluing performance it is characterised in that bearing according to a kind of irradiation of claim 1
In the diaphragm of pole, the mass ratio of material with carbon element, bonding agent and conductive agent is 96:2:2.
7. improve the method for lithium battery Kynoar gluing performance it is characterised in that bearing according to a kind of irradiation of claim 1
Bonding agent in the diaphragm of pole at least includes Kynoar (PVDF), and content is the gross weight of negative electrode active material layer
0.05%～5%；It is further preferred that the content of negative pole bonding agent is the 0.5%～4% of negative electrode active material layer gross weight.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101127392A (en) * | 2006-08-17 | 2008-02-20 | 李鑫 | A secure lithium ion electric core and its making method |
| CN101150182A (en) * | 2006-09-18 | 2008-03-26 | 深圳市比克电池有限公司 | Lithium ion battery electrode slice, electric core and its making method |
| CN102604274A (en) * | 2012-01-20 | 2012-07-25 | 常州回天新材料有限公司 | Modified PVDF (polyvinylidene fluoride) film for solar battery back panel and preparation method of modified PVDF film |
| WO2012167728A1 (en) * | 2011-06-10 | 2012-12-13 | Shenzhen Byd Auto R&D Company Limited | Battery separator and method for preparing the same |
-
2016
- 2016-10-13 CN CN201610895120.1A patent/CN106450327B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101127392A (en) * | 2006-08-17 | 2008-02-20 | 李鑫 | A secure lithium ion electric core and its making method |
| CN101150182A (en) * | 2006-09-18 | 2008-03-26 | 深圳市比克电池有限公司 | Lithium ion battery electrode slice, electric core and its making method |
| WO2012167728A1 (en) * | 2011-06-10 | 2012-12-13 | Shenzhen Byd Auto R&D Company Limited | Battery separator and method for preparing the same |
| CN102604274A (en) * | 2012-01-20 | 2012-07-25 | 常州回天新材料有限公司 | Modified PVDF (polyvinylidene fluoride) film for solar battery back panel and preparation method of modified PVDF film |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200111B (en) * | 2018-11-16 | 2021-03-23 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200107A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| WO2020098792A1 (en) * | 2018-11-16 | 2020-05-22 | 宁德时代新能源科技股份有限公司 | Positive electrode piece and electrochemical device |
| CN111200131A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200114B (en) * | 2018-11-16 | 2021-06-08 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200111A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200110A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200112B (en) * | 2018-11-16 | 2021-06-08 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111200112A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Positive pole piece and electrochemical device |
| CN111199833A (en) * | 2018-11-16 | 2020-05-26 | 宁德时代新能源科技股份有限公司 | Electrochemical device |
| US11575134B2 (en) | 2018-11-16 | 2023-02-07 | Contemporary Amperex Technology Co., Limited | Positive electrode plate and electrochemical device |
| US11189821B2 (en) | 2018-11-16 | 2021-11-30 | Contemporary Amperex Technology Co., Limited | Electrochemical device |
| US11196044B2 (en) | 2018-11-16 | 2021-12-07 | Contemporary Amperex Technology Co., Limited | Positive electrode plate and electrochemical device |
| US11349124B2 (en) | 2019-06-03 | 2022-05-31 | Ningde Amperex Technology Limited | Electrochemical device |
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| WO2022041977A1 (en) | 2020-08-26 | 2022-03-03 | 浙江衢州巨塑化工有限公司 | Copolymerized pvdf resin for lithium battery binder and preparation method therefor |
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