CN106450327B - A method of irradiation improves lithium battery Kynoar gluing performance - Google Patents
A method of irradiation improves lithium battery Kynoar gluing performance Download PDFInfo
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- CN106450327B CN106450327B CN201610895120.1A CN201610895120A CN106450327B CN 106450327 B CN106450327 B CN 106450327B CN 201610895120 A CN201610895120 A CN 201610895120A CN 106450327 B CN106450327 B CN 106450327B
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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
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A method of irradiation improves lithium battery Kynoar gluing performance, belongs to technical field of lithium batteries.Preparation contains the lithium battery of Kynoar (PVDF) binder, entire battery is placed under electron accelerator or lithium ion battery is integrally irradiated on device under the beam of dynamitron, so that irradiation dose is 20~200kGy, radiation dose rate is 50~15000Gy/s, so that PVDF is partial cross-linked, to change its gluing performance, reduce cell thickness expansion rate, the capacity retention ratio of battery is improved, and then improves stability test, extends the service life of battery.
Description
Technical field
The invention belongs to technical field of lithium batteries, are related to a kind of side of irradiation raising lithium battery Kynoar gluing performance
Method.
Background technique
The energy is the material base that the mankind depend on for existence and development.Fossil fuel (coal, petroleum, natural gas) is always the mankind
The main body of using energy source.With the rapid development of society, the non-renewable of fossil fuel, reserves are limited and combustion process causes
Environmental pollution the problems such as gradually highlight.It is converted by natural energies such as wind energy, solar energy, water power energy, geothermal energy, ocean energies
The electric power of acquisition can not large-scale application because of stability and poor continuity.Battery, especially secondary cell are used as will be discontinuous
Electric power store the energy storage medium that smoothly releases again in application, realize new energy effective use.
Lithium ion battery is developed by lithium battery.Lithium battery is a kind of living as cathode using lithium metal or lithium alloy
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
Most negative (- 3.045V, vs.SHE), density minimum (0.53g cm-3), electrochemical equivalent highest (0.26g Ah-1) and theoretical specific volume
Measure highest (3861mAh g-1) metallic element.So battery has high operating voltage, height when using lithium metal as cathode
Energy density and power density.Is started to the research of lithium battery, lithium ion battery is at present with its ratio the 1960s and 1970s
Energy is high, power density is high, have extended cycle life, self discharge is small, cost performance ratio has become 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 car headed by tesla, to alleviate environmental pressure, mixing for battery and machine power is competitively supported in countries in the world
It closes electric car (HEV), such commercial automobile gradually increases.Lithium ion battery, core component is usually by following components
Composition: anode, cathode, electrolyte, diaphragm and auxiliary accessories.Wherein positive and negative anodes are the cores of lithium ion battery, are lithium
Ion provides the carrier of insertion and abjection.The lithium ion battery being commercialized on the market, usually soft bag lithium ionic cell.Electricity
For the anode in pond frequently with oleaginous system, active material is cobalt acid lithium (LiCoO2), binder is Kynoar (PVDF), molten
Agent is N-Methyl pyrrolidone (NMP)；The negative electrode active material of battery is natural graphite, artificial graphite, mesocarbon microspheres
(CMS) or mixture.It can be generally divided into aqueous and oleaginous system, wherein water-based system uses CMC/SBR (styrene-fourth two
Alkene rubber) it is used as binder, there is environmental protection, advantage at low cost, and it is bonding agent that oleaginous system, which generallys use PVDF, solvent is
NMP, the advantage of oleaginous system are that the dynamic performance of battery and cryogenic property are more preferable.
Important component of the bonding agent as battery plus-negative plate material at least plays in general charge and discharge process
Several basic roles below: 1) adhesion activity substance (especially powder)；2) adhere to active material with collector；3) exist
It is risen in charge and discharge process and saves adhesion activity substance (especially powder) and adhere to active material with collector；4) in life
Pulpous state is formed during producing, and is conducive to coating etc..Bonding agent as lithium battery, it is necessary to have following performance: 1) good heat-resisting
Property, lithium ion need strict 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, otherwise expansion as few as possible can gradually lose bonding effect；3) electrochemistry
To oxidisability anode and reproducibility cathode chemical stabilization chemistry, electrochemical reaction do not occur for stability；4) have relatively high
Electronic and ionic electric conductivity；5) dosage is few, cheap, and processability is good.
Contain-CF on PVDF strand2, dielectric constant is higher, is conducive to the dissociation of lithium salts, has mechanical property good, electric
Stable chemical performance, it is good to the stability of electrode the advantages that, while the polymer has typical fluoropolymer-containing stability,
Interaction group on polymer chain can generate a unique polarity.The polarity can influence polymer solubility and lithium ion,
Interaction force between active position and metal collector.PVDF is for anodes a variety of in lithium battery, negative electrode material ratio simultaneously
It is more stable, just react with lithium at 200 degree or more, except the safe handling range of battery, excellent performance make its at
For the major product in commercial battery.PVDF molecular weight is differed from 300,000~3,000,000, and mainly there is French A Kema in manufacturer
(Arkema) PVDFHSV900, Belgian Su Wei (Solvay) 5130, Japanese Wu Yu chemistry KFl300, U.S. 3M, Shanghai three are liked
Rich PVDF FR921-2 etc..Anode, cathode film mixing in bonding agent content used to discharge capacity, high-rate discharge ability
There is great influence with cycle life, internal resistance.When PVDF dosage is less, in the case where ensuring adhesive effect, electrode activity
Material utilization will be high, and initial discharge capacity is just high, but unfavorable to cycle performance of battery；PVDF dosage is very few, and cathode exists
Impregnated in nipping process or through electrolyte it is easy to fall off, it is positive then since specific gravity is larger, slurry is easy to settle in coating process
Layering；When PVDF dosage is more, electrode active material utilization rate is low, and discharge capacity is low, and battery polarization internal resistance increases, discharge platform
It reduces, it is unfavorable to high-multiplying power discharge, but cyclical stability improves.Therefore anode PVDF content is with the 1~5% of solid phase total weight
Preferably, cathode PVDF content is advisable with the 1~7% of solid phase total weight.In existing goods, since PVDF crystallinity is high, the meeting in NMP
Slowly swelling, bonding force gradually decrease, and battery can be made to decay in cyclic process fastly, and resistance increases fastly, influence performance and electricity
Pond service life.Therefore, it needs to be modified PVDF, solves industry rigid demand.
Irradiation grafting modification is to be grafted some monomers or oligomer in polymer surfaces using irradiation, reaches change material
The purpose of energy.It is an important method of macromolecule material surface modification, because of its unique advantage, on a variety of high molecular materials all
There is preferable application.It is modified that irradiation grafting is also widely used in PVDF.For PVDF, it is (first no matter to be grafted onto main chain method
First synthesis has the main polymer chain and side chain of reactive functional groups, by the chemical reaction between two functional groups, by polymer
Side chain is introduced on main polymer chain) or main chain Graft Method (synthesis has the main polymer chain for causing activated centre first,
Then cause second of monomer by the activated centre on main chain to be polymerize), PVDF can be modified well, because
This researchers can assign the superior performance of PVDF by different grafted chains.To irradiation grafting product the study found that spoke
The polymer obtained according to grafting is highly stable, has excellent performance, is conducive to permanent effectiveness in the devices.
Battery material bonding agent needs heat-resisting, solvent resistant, stabilization, therefore cannot have other impurities infiltration in use
Out, it is the most suitable for selecting irradiation grafting method.Direct or indirect graft modification is carried out to PVDF thin film, overcomes its crystallization
After degree height, expansion the disadvantages of bonding force variation, aging, 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, to reduce swellability, so that
Cell thickness is stablized, and 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
Than having the characteristics that own.1) graft reaction that irradiance method causes is more than conventional method.Such as 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, especially in energy
Height irradiates under conditions of penetration power is strong, free radical can be formed uniformly extensively in entire solid fabric, convenient for graft reaction
It carries out.2) ionizing radiation can be by the non-selective absorption of substance.In principle, irradiation grafting technology can be applied to any pair of polymerization
The graft copolymerization of one monomer system of object.3) irradiation grafting is easier to carry out, and easy to operate, can also under room temperature even low temperature
It completes.Meanwhile can be reacted by adjusting the methods of dosage, dosage rate, monomer concentration to control, thus the grafting needed
Speed, grafting rate and grafting concentration (surface or bulk graft).4) irradiation grafting reaction does not need extraneous introducing initiator, therefore
There is no initiator residual, available cleaning, safe graft copolymer, and ensure the purity of polymer.
PVDF is because of its distinctive physicochemical properties, and there are many graft-modified polymers to be applied to the devices such as battery
In, existing document is concentrated mainly on modified PVDF membrane for directions such as proton exchanges, although present commercial batteries are wide
The general bonding agent for using PVDF as positive electrode and negative electrode material, but the work of radiation modification PVDF bonding agent yet there are no report
Road.The dosage of PVDF is referred in the patent of a small amount of company, and mix the technique being film-made with other powder, it was also proposed that PVDF
As the problems such as viscosity existing for bonding agent is inadequate and dilatancy, but particularly suitable process is found not yet
[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 property in lithium ion battery
Case.
Summary of the invention
The present invention provides a kind of scheme by radiation modification battery PVDF gluing performance, by simply irradiating, energy
The performance of modified adhesive, improves the performance of battery.
Concrete scheme is as follows: including the following steps
(1) lithium battery is prepared, battery structure is soft bag lithium ionic cell, and positive plate, diaphragm and negative electrode tab are rolled up in order
It is coiled into battery core, with aluminium profiles film by battery core closedtop and side seal, liquid injection port perfusion electrolyte is left, using works such as chemical conversion, capacity
Lithium ion battery is made in sequence；
Wherein positive plate includes plus plate current-collecting body and coated in the positive diaphragm on the plus plate current-collecting body, positive diaphragm packet
Positive active material, bonding agent and conductive agent are included, positive electrode active materials are preferably LiMn2O4, cobalt acid lithium, nickle cobalt lithium manganate etc. one
Kind 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 the one or more of carbon nanotube；
Battery cathode sheet includes negative current collector and the cathode membrane coated in the negative current collector surface, cathode membrane
Including carbon material, bonding agent and conductive agent；Carbon material be preferably natural graphite, carbonaceous mesophase spherules, artificial graphite one kind 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 kinds of mixtures.
(2) lithium ion battery obtained by step (1) is integrally placed to electronics and accelerated by the radiation modification method of lithium ion battery
Lithium ion battery is integrally irradiated under device or under the beam of dynamitron on device, irradiation apparatus parameter is adjusted, makes
Irradiation dose be 20~200kGy, preferably 30~120kGy, radiation dose rate be 50~15000Gy/s, preferably 2000
~10000Gy/s carries out the radiation treatment of doses to lithium ion battery, so that PVDF is partial cross-linked, to change its glue
Stickiness energy, and then improve stability test.Dosage is too low, and crosslinking is insufficient, and intensity is inadequate, and gluing performance is difficult to improve, dosage
Excessively high, the degree of cross linking is too big, and the flexibility of PVDF is inadequate, and gluing performance can also be deteriorated, and is unfavorable for the multiple circulation of battery.
The preparation of above-mentioned steps (1) lithium ion battery the following steps are included:
Step 1: 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 N-Methyl pyrrolidone (NMP), is stirred evenly, is obtained anode sizing agent.The anode slurry that will be obtained
Material is coated on certain thickness plus plate current-collecting body as on aluminium foil, and dry, cold pressing obtains compacted density in 1.4~1.6g/cm3
Pole piece, using cut-parts, soldering polar ear obtains 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 negative electrode slurry, is then coated on negative electrode slurry negative
On the collector of pole, such as copper foil, cathode membrane is formed after dry, by cold pressing, slitting, soldering polar ear obtains negative electrode tab.
Step 3: the electrolyte of lithium ion battery, by methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate
Ester (EC), propene carbonate (PC) are uniformly mixed according to a certain percentage, and certain density lithium hexafluoro phosphate is added as solute, system
At electrolyte.
Step 4: diaphragm, using polyethylene porous membrane, perforated membrane is with a thickness of 15~20 μm.
Step 5: obtained positive plate, negative electrode tab and diaphragm are wound into battery core in order, use aluminium by the assembling of lithium battery
Battery core closedtop and side seal are left liquid injection port perfusion electrolyte, lithium-ion electric are made using processes such as chemical conversion, capacity by type film
Pond.
It is preferred that the mass ratio of positive active material, bonding agent and conductive agent is 95:3:2 in positive diaphragm；Bonding agent is preferred
For one of Kynoar (PVDF), polyvinyl alcohol bonding agent, polyurethane adhesive, epoxy resin adhesive or several
Mixture；Bonding agent further preferably in anode diaphragm includes at least Kynoar (PVDF), and content is that anode is living
The 0.5%~6% of the total weight of property material layer；It is further preferred that the content of positive bonding agent PVDF is positive active material
The 1%~5% of layer total weight.
It is preferred that the mass ratio of carbon material, bonding agent and conductive agent is 96:2:2 in cathode membrane；It is preferred that in cathode membrane
Bonding agent includes at least Kynoar (PVDF), and content is the 0.05%~5% of the total weight of negative electrode active material layer；Into
Preferably, the content of cathode bonding agent is the 0.5%~4% of negative electrode active material layer total weight to one step.
Compared with the existing technology, the whole irradiation of battery, reduces processing program, uses ground nanometer accelerator or electronics
Accelerator, it is safer than cobalt source accelerator, it is also easier to control device parameter, to control the crosslinking degree of PVDF.This skill
Art scheme is not likely to produce stripping so that PVDF adhesive has better gluing performance in battery core by improving the degree of cross linking of PVDF
From, swellability is reduced, so that cell thickness is stablized, it is advantageous to the circulatory system of battery, energy density is maintained, improves and uses the longevity
Life.Key innovations of the invention are that lithium battery anode piece, cathode pole piece preparation process are simple, do not need to PVDF into
Row heat treatment is chemically treated to adjust its crystal form or Film Morphology, it is only necessary to directly put assembled lithium ion battery
Whole irradiation is carried out under dynamitron or electron accelerator.Modified technique is simple and efficient, and irradiation time is short, effect
It is good.Cobalt source relative to early stage irradiates, and production efficiency is higher, safer.Can raising PVDF rapidly and efficiently it is negative in lithium battery
Adhesive property in the pole piece of pole, so that thickness swelling of the battery after circulation is multiple is substantially reduced, the capacity for improving battery is protected
Holdup, substantially prolongs the service life of battery, so that the user satisfaction of consumer be greatly improved, and then improves such
The market position of battery.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1:
The preparation of based lithium-ion battery positive plate:
By positive active material cobalt acid lithium, nickle cobalt lithium manganate, conductive carbon, binder PVDF according to 70:25:3:2 quality
Than being blended in solvent NMP, stirs evenly, obtain anode sizing agent.Obtained anode sizing agent is coated on 9 μm of aluminium foil, is done
Dry, cold pressing obtains compacted density in 1.5g/cm3Pole piece, using cut-parts, soldering polar ear obtains positive plate.
The preparation of anode plate for lithium ionic cell:
By negative electrode active material natural graphite, conductive carbon, binder PVDF (whole melting temperatur is 160 degree) according to mass ratio
96:2:2 is added in solvent NMP, after mixing, obtains negative electrode slurry, then negative electrode slurry is applied to the metal for being coated in 8 μ m-thicks
The two sides of copper foil is dried into the cathode pole piece with certain suppleness, and by cold pressing, slitting, soldering polar ear obtains negative electrode tab.
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:
The mass ratio of 1:0.5:0.5 is uniformly mixed, and lithium hexafluoro phosphate (LiPF is added6) it is used as solute, make the concentration of lithium hexafluoro phosphate
For 1mol/L, electrolyte is made.
Diaphragm uses polyethylene porous membrane, and perforated membrane is with a thickness of 16 μm.
The preparation of lithium battery:
Positive plate, negative electrode tab and diaphragm are wound into battery core in order, with aluminium profiles film by battery core closedtop and side seal, left
Electrolyte is perfused in liquid injection port, and lithium ion battery is made using processes such as chemical conversion, capacity.
The irradiation of lithium ion battery:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set carries out radiation treatment to lithium ion battery, irradiation dose 40kGy makes so that dosage rate is 5000Gy/s
It is partial cross-linked to obtain PVDF.Lithium ion battery is taken out from trolley later, tests battery performance.
Embodiment 2:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set carries out radiation treatment to lithium ion battery, irradiation dose 70kGy makes so that dosage rate is 5000Gy/s
It is partial cross-linked to obtain PVDF.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 3:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 100kGy,
So that PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 4:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 130kGy,
So that PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 5:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set carries out radiation treatment to lithium ion battery, irradiation dose 40kGy makes so that dosage rate is 8000Gy/s
It is partial cross-linked to obtain PVDF.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 6:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set carries out radiation treatment to lithium ion battery, irradiation dose 70kGy makes so that dosage rate is 8000Gy/s
It is partial cross-linked to obtain PVDF.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 7:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set so that dosage rate be 8000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 100kGy,
So that PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 8:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under dynamitron on device, trolley loads, and orderly tiles.Optionally
That meter of accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, are filled under accelerator energy and accelerator beam by adjusting
The travel speed set so that dosage rate be 8000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 130kGy,
So that PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 9:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under electron accelerator on device, trolley loads, and orderly tiles.Select electronics
Accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator beam
Travel speed so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 40kGy so that
PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 10:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under electron accelerator on device, trolley loads, and orderly tiles.Select electronics
Accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator beam
Travel speed so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 70kGy so that
PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 11:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under electron accelerator on device, trolley loads, and orderly tiles.Select electronics
Accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator beam
Travel speed so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 100kGy so that
PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Embodiment 12:
The irradiation of lithium ion battery unlike the first embodiment:
Lithium ion battery is placed under the beam under electron accelerator on device, trolley loads, and orderly tiles.Select electronics
Accelerator, accelerator energy 5MeV adjust irradiation apparatus parameter, by adjusting device under accelerator energy and accelerator beam
Travel speed so that dosage rate be 5000Gy/s, to lithium ion battery carry out radiation treatment, irradiation dose 130kGy so that
PVDF is partial cross-linked.Lithium ion battery is taken out from trolley later, tests battery performance.
Remaining is the same as embodiment 1.
Comparative example 1:
Preparing for lithium battery is same as Example 1, the difference is that comparative example is without radiation modification.Lithium battery is carried out to calculate
Terminate.
For check test effect, the battery in all embodiment and comparative examples uses 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:
The lithium battery of method preparation and radiation modification using embodiment 1 to 12 and comparative example 1 is split, is used
The reversed stripping method of 180 degree carries out cohesive force test, and 5 samples of every group of selection test every group of sample, are averaged carry out bonding force
Comparison, acquired results are shown in Table one.
Table 1: the negative electrode tab obtained after splitting using battery prepared by the method for embodiment 1 to 12 and comparative example 1 is glued
Relay test result.
As can be seen from Table 1, it is apparently higher than using the bonding force of the negative electrode tab of the method for the present invention preparation using comparative example
The negative electrode tab of method preparation, this shows that method of the invention can significantly improve the bonding force of negative electrode tab.
In battery industry, PVDF will be slow swelling in NMP, and bonding force gradually decreases, and battery can be made in cyclic process
Middle decaying is fast, and resistance increases fastly, influences performance and battery.Radiation modification is substantially by properly increasing PVDF
The degree of cross linking, to increase interface wellability to improve cohesive force and cohesive force, so that swellability is reduced, so that cell thickness is steady
It is fixed, energy density is maintained, is improved service life.
Following at 25 DEG C is carried out to the lithium battery of method preparation and radiation modification using embodiment 1 to 12 and comparative example 1
Ring test, and after recording 100 circulations, 200 circulations, 400 circulations (rate of charge and discharge-rate be 0.5C) respectively
Battery thickness swelling, 5 samples of every group of selection test every group of sample, be averaged the comparison for carrying out thickness swelling,
Acquired results are shown in Table 2.
Table 2: the circulating battery expansion rate test result prepared using the method for embodiment 1 to 12 and comparative example 1
Table 2 the results show that using the method for the present invention, it is irradiated after battery, the thickness after circulating battery is multiple is swollen
Swollen obviously to become smaller, after also illustrating irradiation to a certain extent, the gluing performance of PVDF is improved, so that pole piece has higher bonding
Performance reduces so that the expansion of negative electrode tab rebounds, and further reduced the circulation expansion of battery.Service life after lithium ion battery circulation
It is obviously improved.
Following under 45 degree is carried out to the lithium battery of method preparation and radiation modification using embodiment 1 to 12 and comparative example 1
Ring test, and the capacity retention ratio of the battery after 100 circulations, 200 circulations, 400 circulations, every group of selection 5 are recorded respectively
A sample tests every group of sample, is averaged the comparison for carrying out thickness swelling, and acquired results are shown in Table 3.
Table 3: the circulating battery plot ratio test result prepared using the method for embodiment 1 to 12 and comparative example 1
Table 3 the results show that using the method for the present invention, it is irradiated after battery, the battery after circulating battery is multiple holds
Amount conservation rate is obviously improved, and shows that PVDF adhesive passes through after cross-linking radiation, and the stability of battery improves, and deformation rate is small,
Battery capacity conservation rate is high, and the service life is obviously improved after lithium ion battery circulation.
The announcement and guidance of book according to the above description, those skilled in the art in the invention can also be to above-mentioned experiment sides
Case carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into claim and protection scope of the invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of method that irradiation improves lithium battery Kynoar gluing performance, which comprises the following steps:
(1) lithium battery is prepared, battery structure is soft bag lithium ionic cell, and positive plate, diaphragm and negative electrode tab are wound into order
Battery core leaves liquid injection port perfusion electrolyte, is made using chemical conversion, capacity process with aluminium profiles film by battery core closedtop and side seal
Lithium ion battery；
Wherein positive plate includes plus plate current-collecting body and coated in the positive diaphragm on the plus plate current-collecting body, and positive diaphragm includes just
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 of kind；Bonding agent is Kynoar (PVDF), polyvinyl alcohol bonding agent, polyurethane adhesive, adhering with epoxy resin
One of agent or several mixtures；Conductive agent is the one or more of conductive black, electrically conductive graphite and carbon nanotube；
Battery cathode sheet includes negative current collector and the cathode membrane coated in the negative current collector surface, and cathode membrane includes
Carbon material, bonding agent and conductive agent；Carbon material is the one or several kinds of natural graphite, carbonaceous mesophase spherules, artificial graphite
Mixture；Bonding agent is PVDF, and conductive agent is one or more kinds of mixtures of conductive black, graphene, carbon fiber；
(2) lithium ion battery obtained by step (1) is integrally placed under electron accelerator by the radiation modification method of lithium ion battery
Or lithium ion battery is integrally irradiated on device under the beam of dynamitron, irradiation apparatus parameter is adjusted, so that spoke
It is 20~200kGy according to dosage, radiation dose rate is 50~15000Gy/s, at the irradiation of lithium ion battery progress doses
Reason to change its gluing performance, and then improves stability test so that PVDF is partial cross-linked.
2. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that spoke
It is 30~120kGy according to dosage, radiation dose rate is 2000~10000Gy/s.
3. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that step
Suddenly (1) lithium ion battery preparation the following steps are included:
Step 1: the preparation of based lithium-ion battery positive plate, by positive active material, bonding agent and conductive agent according to certain quality
Than mixing in a solvent, stirs evenly, obtain anode sizing agent；Obtained anode sizing agent is coated on certain thickness anode collection
Dry on body, cold pressing obtains compacted density in 1.4~1.6g/cm3Pole piece, using cut-parts, soldering polar ear obtains anode
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 mixing in a solvent, after mixing, obtain negative electrode slurry, negative electrode slurry be then coated on negative current collector
On, such as copper foil, cathode membrane is formed after dry, by cold pressing, slitting, soldering polar ear obtains negative electrode tab；
Step 3: the electrolyte of lithium ion battery, by methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate
(EC), propene carbonate (PC) is uniformly mixed according to a certain percentage, and certain density lithium hexafluoro phosphate is added as solute, is made
Electrolyte；
Step 4: diaphragm, using polyethylene porous membrane, perforated membrane is with a thickness of 15~20 μm；
Step 5: obtained positive plate, negative electrode tab and diaphragm are wound into battery core by the assembling of lithium battery in order, thin with aluminium profiles
Battery core closedtop and side seal are left liquid injection port perfusion electrolyte, lithium ion battery are made using processes such as chemical conversion, capacity by film.
4. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that just
Positive active material in the diaphragm of pole, bonding agent, conductive agent mass ratio be 95:3:2.
5. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that just
Bonding agent in the diaphragm of pole includes at least Kynoar PVDF, and content is the 0.5% of the total weight of positive electrode active material layer
~6%.
6. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that negative
The mass ratio of carbon material, bonding agent and conductive agent is 96:2:2 in the diaphragm of pole.
7. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that negative
Bonding agent in the diaphragm of pole includes at least Kynoar PVDF, and content is the 0.05% of the total weight of negative electrode active material layer
~5%.
8. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that just
Conductive black in pole piece is selected from superconduction carbon black, and conductive black is selected from superconduction carbon, acetylene black in battery cathode sheet.
9. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that just
The content of pole bonding agent PVDF is the 1%~5% of positive electrode active material layer total weight.
10. the method for improving lithium battery Kynoar gluing performance according to a kind of irradiation of claim 1, which is characterized in that
The content of cathode bonding agent is the 0.5%~4% of negative electrode active material layer total weight.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN112234208B (en) | 2019-06-03 | 2021-11-23 | 宁德新能源科技有限公司 | Electrochemical device |
| CN111600075A (en) * | 2020-05-06 | 2020-08-28 | 中国科学院高能物理研究所 | Method for improving electrolyte resistance of binder in lithium battery negative pole piece through irradiation |
| 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 |
| CN114497455A (en) * | 2020-10-27 | 2022-05-13 | 荣盛盟固利新能源科技有限公司 | Method for improving lithium ion battery pole piece cohesiveness by ray irradiation and lithium ion battery pole piece |
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