CN109755464A - Electrode pole piece, electrochemical device and safety coating - Google Patents
Electrode pole piece, electrochemical device and safety coating Download PDFInfo
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- CN109755464A CN109755464A CN201711091767.XA CN201711091767A CN109755464A CN 109755464 A CN109755464 A CN 109755464A CN 201711091767 A CN201711091767 A CN 201711091767A CN 109755464 A CN109755464 A CN 109755464A
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- pole piece
- inorganic filler
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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
Abstract
The invention relates to an electrode plate, an electrochemical device and a safety coating. The electrode plate comprises a current collector, an electrode active material layer and a safety coating arranged between the current collector and the electrode active material layer, wherein the safety coating comprises a polyvinylidene fluoride and/or polyvinylidene chloride polymer matrix, a conductive material and an inorganic filler. The electrode pad can rapidly open a circuit when an electrochemical device (such as a capacitor, a primary battery or a secondary battery, etc.) is in a high-temperature condition or an internal short circuit occurs, thereby improving the high-temperature safety of the electrochemical device.
Description
Technical field
The invention belongs to electrochemical technology field, it is more particularly related to a kind of electrode plates and including the electricity
The electrochemical appliance of pole pole piece.
Background technique
Energy density is big, output power is high, has extended cycle life the advantages that small with environmental pollution due to having for lithium ion battery
And it is widely used in electric car and consumer electronics product.However lithium ion battery is being squeezed, is colliding or is wearing
It is easy to that kindling, explosion occurs when the abnormal conditions such as thorn, so as to cause serious harm.Therefore the safety problem of lithium ion battery is very
It limits to big degree the application of lithium ion battery and popularizes.
Abundant experimental results show that battery internal short-circuit is the basic place for causing lithium ion battery security risk.In order to keep away
Exempt from that battery internal short-circuit occurs, researchers attempt to improve in terms of many, including the characteristic using ptc material come
Promote the research in terms of the security performance of lithium ion battery.PTC (Positive Temperature Coefficient) material
That is positive temperature coefficient thermo-sensitive material, the characteristic that there is resistivity to increase with temperature raising for it, when temperature is more than certain temperature
When, its resistivity increasing rapidly in step evolution.
In the research in terms of security performance of the characteristic using ptc material to promote lithium ion battery, some researchs are
Ptc material is added in the active material layer of battery.When battery temperature increases, the resistance of ptc material increases, so as to cause whole
The resistance of a active material layer becomes larger, even more so that the conductive path of entire active material layer is destroyed, to play power-off, resistance
The only safe effect that electrochemical reaction continues.However in this improved procedure, the PTC material that is added in active material layer
Material can have a adverse impact to the chemical property of battery.
Also some researchs are that ptc layer (safety painting is separately provided between the collector and active material layer of battery
Layer).When battery temperature increases, the resistance of ptc layer increases, so that resistance increases between collector and active material layer
Greatly, it even powers off, to play the safe effect for preventing electrochemical reaction from continuing.However in this improved procedure,
When ptc layer surface coats active material slurry, the solvent (such as NMP) in slurry can be molten by the ptc material in PTC layers
Solution, and enter in the active material layer of upper layer, not only make PTC layers to lose PTC effect, but also electrical property can be deteriorated.In addition, in pole piece
In compacting step in manufacturing process, ptc layer is easily extruded into edge, and active material layer is caused directly to connect with collector
Touching, to lose the effect for improving security performance.In addition, the performances such as the response speed of ptc layer, effect of blocking electric current are equal
It needs to greatly improve.
In view of this, it is necessory to provide it is a kind of be able to solve the above problem have improved safety and battery performance
The pole piece and battery of (such as cycle performance).
Summary of the invention
It is an object of the present invention to: a kind of pole with improved safety and electrical property (such as cycle performance) is provided
Piece and electrochemical appliance.
It is another object of the present invention to: it provides one kind has both good safety and electrical property (such as cycle performance)
Pole piece and electrochemical appliance.
The further object of the present invention is: providing a kind of electrical property (such as cyclicity with good safety, improvement
Can), the excellent performances such as workability be suitable for being mass produced and the pole piece and electrochemical appliance of application.
The present invention provides a kind of electrode plates, including collector, electrode active material layers and it is set to collector and electricity
Safety coatings between the active material layer of pole, the safety coatings include macromolecule matrix, conductive material and inorganic filler, described
Macromolecule matrix is to gather inclined fluoroolefins and/or gather inclined chloro-alkenes macromolecule matrix, wherein the total weight based on safety coatings: described
The weight percent of macromolecule matrix is 35wt%-75wt%, preferably 50wt%-75wt%；The weight of the conductive material
Percentage is 5wt%-25wt%, preferably 5wt%-15wt%；The weight percent of the inorganic filler is 10wt%-
60wt%, preferably 15wt%-45wt%.Preferably, the conductivityσ of the inorganic filler meets: 10-3S/m≤σ≤102S/
m。
The present invention also provides a kind of electrochemical appliances comprising electrode plates of the invention, the electrochemical appliance are excellent
It is selected as capacitor, one-shot battery or secondary cell.
The present invention also provides a kind of electrode plates safety coatings, it includes: macromolecule matrixes, conductive material and inorganic
Filler, the macromolecule matrix is to gather inclined fluoroolefins and/or gather inclined chloro-alkenes macromolecule matrix, based on the total of the safety coatings
Weight, the weight percent of the macromolecule matrix are 35wt%-75wt%, preferably 50wt%-75wt%；The conduction material
The weight percent of material is 5wt% to 25wt%, preferably 5wt%-15wt%；The weight percent of the inorganic filler is
10wt%-60wt%, preferably 15wt%-45wt%.Preferably, the conductivityσ of the inorganic filler meets: 10-3S/m≤σ
≤102S/m。
Detailed description of the invention
With reference to the accompanying drawings and detailed description, to electrode plates of the invention, electrochemical appliance and its advantages
It is described in detail.
Fig. 1 is according to the structural schematic diagram of the anode pole piece of the embodiment of the present invention, wherein 10-collectors；14-anodes are living
Property material layer；12-safety coatings (i.e. PTC safety coatings).
Specific embodiment
The invention discloses a kind of electrode plates, including collector, electrode active material layers and it is set to collector and electricity
Safety coatings between the active material layer of pole, the safety coatings include to gather inclined fluoroolefins and/or to gather inclined chloro-alkenes polymer-based
Body, conductive material and inorganic filler.
The electrode plates can be anode pole piece, cathode pole piece, it is preferred that anode pole piece is (because anode pole piece is in electricity
Safety problem caused by the adstante febre of pond is often more prominent).When obviously, as anode pole piece, in electrode plates of the invention
Electrode active material layers are anode active material layer；And electrode activity when as cathode pole piece, in electrode plates of the invention
Material layer is anode active material layer.Fig. 1 shows the structural schematic diagram of the anode pole piece of some embodiments according to the present invention,
In 10-collectors, 14-anode active material layers, 12-safety coatings (i.e. PTC safety coatings).
Although it can be readily appreciated that being that PTC safety coatings only are arranged in the single side of positive pole collector 10 shown in Fig. 1
12 and anode active material layer 14, but in other embodiments, plus plate current-collecting body 10 can be in two-sided setting PTC safety coatings 12
With anode active material layer 14.
In the present invention, gather inclined fluoroolefins as the described of the macromolecule matrix material of safety coatings and/or gather inclined chlorine alkene
Hydrocarbon refers to Kynoar (PVDF), Vingon (PVDC), modified PVDF or modified PVDC.For example, described
Gathering inclined fluoroolefins and/or gather inclined chloro-alkenes can be total selected from PVDF, carboxyl acid modified PVDF, acrylic acid modified PVDF, PVDF
Polymers, PVDC, carboxyl acid modified PVDC, acrylic acid modified PVDC, PVDC copolymer.
In the coating with PTC effect being traditionally used in battery, usually using polyethylene, polypropylene or ethylene propylene
Alkene copolymer etc. is used as PTC basis material, needs that bonding is additionally added in PTC basis material and conductive material in this case
The caking property of agent, the too small then coating of binder content and collector is poor, and binder content is excessive, influences whether PTC effect
Respond the performances such as temperature and response speed.It is exactly a kind of common viscous for gathering inclined fluoroolefins and/or gathering inclined chloro-alkenes (such as PVDF)
Tie agent.As binder in use, the dosage of PVDF will be much smaller than the dosage of basis material.Such as among traditional PTC coating
PVDF binder be usually less than 15% or 10% relative to coating gross weight, it is even lower.Certain documents (such as
CN105594019A, CN06558676A) PVDF itself is also mentioned possible as the use of PTC basis material, but be mostly for reason
By upper conjecture, not using effect of the actual verification PVDF as PTC basis material.Meanwhile other document (such as
[0071] section of CN104823313A) then clearly propose that PVDF is not suitable as the use of PTC basis material.
In the present invention, the safety coatings use being set between collector and electrode active material layers gathers inclined fluoroolefins
And/or gather inclined chloro-alkenes as macromolecule matrix material, it can still play the role of PTC thermistor layer.It is applied relative to safety
Layer total weight, as macromolecule matrix material poly- inclined fluoroolefins and/or gather inclined chloro-alkenes weight percent be 35wt%-
75wt%.This dosage much higher than the poly- inclined fluoroolefins used usually as binder in prior art PTC thermistor layer and/
Or gather the dosage of inclined chloro-alkenes (such as PVDF).
In the present invention, gather inclined fluoroolefins and/or gather inclined chloro-alkenes material and actually play the role of both sides, both
As PTC matrix, and as binder.This avoid the differences due to binder and PTC basis material, and caused by painting
The influence of the caking property, the response temperature of PTC effect and response speed etc. of layer.
Secondly, PTC can be played by gathering inclined fluoroolefins and/or gathering inclined chloro-alkenes material and the safety coatings of conductive material composition
The effect of thermal resistor layer, actuation temperature range is appropriate, can be 80 DEG C to 160 DEG C, therefore can improve the height of battery well
Warm security performance.
In addition, the poly- inclined fluoroolefins of the macromolecule matrix material as safety coatings and/or gather inclined chloro-alkenes, both conducts
PTC matrix, and as binder, relatively thin safety coatings are prepared to also help, and do not influence the caking property of safety coatings.
In addition, the solvent (such as NMP) or electrolyte in the electrode active material layers in safety coatings upper layer can be to peaces
High molecular material in full coat layer generates the adverse effects such as dissolution, swelling, for the safety of the PVDF only containing consumption of binder
For coating, caking property variation is easily caused；And for the safety coatings of the application, due to gathering inclined fluoroolefins and/or gathering
The content of inclined chloro-alkenes is larger, therefore this adverse effect is negligible.
In electrode plates of the invention, the total weight based on safety coatings is described to gather inclined fluoroolefins and/or gather inclined chlorine alkene
The weight percent of hydrocarbon macromolecule matrix is 35wt%-75wt%.Content is too small, then can not guarantee safety coatings well
PTC effect；Too high levels, then conductive material and the content of inorganic filler are too small, then also will affect the response speed of safety coatings
Etc. performances.The weight percent for gathering inclined fluoroolefins and/or gathering inclined chloro-alkenes macromolecule matrix is preferably 40wt%-
75wt%, more preferably 50wt%-75wt%.
In the present invention, the safety coatings being set between collector and electrode active material layers also include conductive material.
The conductive material can be selected from least one of conducting carbon-based material, conductive metallic material and conducting polymer materials,
Middle conducting carbon-based material in conductive black, acetylene black, graphite, graphene, carbon nanotube, carbon nano-fiber at least one
Kind；Conductive metallic material is selected from least one of Al powder, Ni powder, bronze；Conducting polymer materials are selected from conductive polythiophene, lead
At least one of voltolisation pyrroles, electrically conductive polyaniline.Conductive material, which can be used alone, one kind or to be applied in combination two or more.
The action principle of safety coatings of the invention are as follows: at normal temperature, safety coatings are by forming between conductive material
Good conductive network carries out electronics conduction；When temperature increases, the volume of macromolecule matrix material starts to expand, conductive material
Spacing increases between particle, and conductive network is partially obstructed, and the resistance of safety coatings is gradually increased；And works as and reach certain temperature
When (such as actuation temperature), conductive network is almost separated, and electric current approach is zero, to protect using the safety coatings
Electrochemical appliance.Therefore, the dosage of conductive material correctly plays a role for PTC layers critically important.In the present invention, relative to peace
The total weight of full coat layer, the weight percent of the conductive material are 5wt% to 25wt%, preferably 5wt% to 15wt%.
Conductive material uses usually in the form of powder or particle.Depending on specific application environment, partial size be can be
5nm-500nm, such as 10nm-300nm, 15nm-200nm, 15nm-100nm, 20nm-400nm, 20nm-150nm etc..
In the present invention, the safety coatings being set between collector and electrode active material layers also include inorganic filler.
It has been found that the solvent when not containing inorganic filler in safety coatings, in the electrode active material layers in safety coatings upper layer
(such as NMP) or electrolyte can generate the adverse effects such as dissolution, swelling to the high molecular material in safety coatings, so that safety applies
Layer can be destroyed, and the performance of PTC effect is influenced.Inventors have found that after being added to inorganic filler in safety coatings, this is inorganic to be filled out
Material is equivalent to a kind of barrier material, to be conducive to eliminate the adverse effects such as above-mentioned dissolution, swelling, is conducive to stablize safety painting
Layer.Guarantee in pole piece compacting process moreover, it has been found that the addition of inorganic filler also helps, safety coatings are unlikely to deform.Cause
The addition of this inorganic filler can guarantee that well safety coatings are steadily between collector and electrode active material layers, prevent
Only collector is directly contacted with electrode active material layers, so as to improve the security performance of battery.
Inventor has also been unexpectedly found that inorganic filler can also improve the performances such as the response speed of safety coatings.Peace
The action principle of full coat layer are as follows: at normal temperature, safety coatings are carried out by the good conductive network formed between conductive material
Electronics conduction；When temperature increases, the volume of macromolecule matrix material starts to expand, and spacing increases between conducting material granule, leads
Electric network is partially obstructed, and the resistance of safety coatings is gradually increased；It is conductive when reaching certain temperature (such as actuation temperature)
Network is almost separated, and electric current approach is zero.However under normal conditions, a kind of dynamic equilibrium is reached inside safety coatings
Afterwards, conductive network is partially restored again, therefore after reaching certain temperature (such as actuation temperature), the resistance of safety coatings is not
It is big that as was expected, and still has the electric current of very little to pass through.Inventors have found that after inorganic filler is added, in macromolecule matrix
After the volume expansion of material, the macromolecule matrix material of inorganic filler and volume increase can act as the effect of barrier conductive network
Fruit.Therefore after inorganic filler is added, within the scope of actuation temperature, safety coatings can preferably generate PTC effect, i.e. high temperature
Lower resistance value is increased speed faster, and PTC response speed is faster.So as to preferably improve the security performance of battery.
Total weight based on safety coatings, the weight percent of the inorganic filler are 10wt%-60wt%.Inorganic filler
Content is too small, is not enough to stablize safety coatings；Content is excessive, then will affect the PTC performance of safety coatings.The weight of inorganic filler
Percentage is preferably 15wt%-45wt%.
Inorganic filler can play the role of stable safety coatings: (1) impeded electrode active material layer in terms of following two
In solvent (such as NMP) or electrolyte in safety coatings high molecular material generate dissolution, swelling etc. adverse effects；(2)
It advantageously ensures that in pole piece compacting process, safety coatings are unlikely to deform.
The inorganic filler is selected from metal oxide, nonmetal oxide, metal carbides, non-metallic carbide, inorganic
The conductive coated modified carbon of at least one of salt or above-mentioned material, conductive metal coating modification or conducting polymer cladding change
At least one of the material of property.
For example, the inorganic filler can be selected from magnesia, aluminium oxide, titanium dioxide, zirconium oxide, silica, carbonization
Silicon, boron carbide, calcium carbonate, alumina silicate, calcium silicates, potassium titanate, barium sulfate, cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickel
Manganese cobalt acid lithium, nickel manganese lithium aluminate, LiFePO4, phosphoric acid vanadium lithium, cobalt phosphate lithium, lithium manganese phosphate, ferric metasilicate lithium, vanadium lithium silicate, silicon
The conductive coated modified carbon of at least one of sour cobalt lithium, manganese silicate of lithium, lithium titanate or above-mentioned material, conductive metal cladding change
At least one of property or the material of conducting polymer coating modification.
As a kind of further improvement of the invention, when the conductivityσ of inorganic filler meets 10-3S/m≤σ≤102S/m
When, additional benefit can be brought.
Inventors have found that the addition of inorganic filler will affect the electric conductivity of safety coatings, and then entire pole may be influenced
The electric conductivity of piece.When the conductivityσ of inorganic filler meets 10-3S/m≤σ≤102When S/m, can make safety coatings battery just
Electric conductivity at a temperature of being often used is improved.If the conductivityσ of inorganic filler is too small, the initial internal resistance of safety coatings and
Internal resistance growth rate can be very high；σ is excessively high, then when reaching PTC actuation temperature, conductive network is not easy to be cut off, it is possible to can not play
Safety effect.In the above conductivity range, battery core internal resistance and internal resistance growth rate very little when normal use, when occur internal short-circuit or
When hot conditions, conductive network can be disconnected rapidly.
It will be appreciated by those skilled in the art that: if the conductivityσ of certain inorganic fillers is unsatisfactory for 10-3S/m≤σ≤
102S/m can then be modified by material commonly used in the art or modified method is made its conductivity meet above-mentioned requirements.
For example, inventor uses positive electro-chemical activity it has been found that when safety coatings of the invention are used for anode pole piece
Material has special advantage as inorganic filler.In this case, inorganic filler is in addition to stable safety coatings above-mentioned
Effect (hinder organic solvent to high molecular material generate dissolution, swelling etc. adverse effects and guarantee that safety coatings are unlikely to deform)
With outside the performances such as response speed for improving safety coatings, further, can also play it is following of both effect: (1) improve
The over-charging of battery: gathering inclined fluoroolefins and/or gathering the PTC painting safely of inclined chloro-alkenes macromolecule matrix, conductive material composition
In coating systems, since electrochemical active material has the characteristics that embedding lithium ionic insertion/deinsertion, at a temperature of normal battery operation, electrification
Learning active material can be used as " the active point " for participating in conductive network, i.e., " active point " in safety coatings increases, overcharging
In the process, electrochemical active material can take off lithium and de- lithium difficulty is increasing, and impedance is continuously increased, therefore when an electric current passes through it,
Heat production power increases, and priming coat temperature is increased speed faster, so that PTC effect response speed is faster, and then can be produced in battery
Raw generation PTC effect before overcharging safety problem, improve battery overcharges safety；(2) charge/discharge capacity is contributed: due to electrochemistry
Active material can contribute certain charge/discharge capacity at a temperature of normal battery operation, therefore may make in normal working temperature
Influence of the lower safety coatings to chemical properties such as the capacity of battery minimizes.Be suitable for this purposes it is particularly preferred just
Pole electrochemical active material is selected from cobalt acid lithium, nickel manganese cobalt acid lithium, nickel manganese lithium aluminate, LiFePO4, phosphoric acid vanadium lithium, cobalt phosphate
Lithium, lithium manganese phosphate, ferric metasilicate lithium, vanadium lithium silicate, cobaltous silicate lithium, manganese silicate of lithium, lithium manganate having spinel structure, spinel-type nickel mangaic acid
At least one of lithium, lithium titanate.
But some common positive electrochemical active material conductivity itself and it is unsatisfactory for 10-3S/m≤σ≤102S/m's
It is required that.Inventors have found that by carrying out conductive coated modified carbon, conductive metal coating modification or conduction to electrochemical active material
Polymer overmold is modified, and the conductivity of electrochemical active material can be made to meet the requirements to being more suitable for the present invention,
And then provide more excellent comprehensive performance.Therefore, in some preferred embodiments, safety coatings of the invention use conductive
Coated modified carbon, conductive metal coating modification or the positive electrochemical active material of conducting polymer coating modification are filled out as inorganic
Material.In further preferred some embodiments, the inorganic filler in safety coatings of the invention is preferably conductive carbon coating
Modified cobalt acid lithium, the nickel manganese cobalt acid lithium of conductive coated modified carbon, the nickel manganese lithium aluminate of conductive coated modified carbon, conductive carbon coating
Modified LiFePO4, the phosphoric acid vanadium lithium of conductive coated modified carbon, the cobalt phosphate lithium of conductive coated modified carbon, conductive carbon coating change
Property lithium manganese phosphate, the ferric metasilicate lithium of conductive coated modified carbon, the vanadium lithium silicate of conductive coated modified carbon, conductive coated modified carbon
Cobaltous silicate lithium, the manganese silicate of lithium of conductive coated modified carbon, the lithium manganate having spinel structure of conductive coated modified carbon, conductive carbon coating
At least one of modified spinel-type nickel ion doped, lithium titanate of conductive coated modified carbon.These conductive coated modified carbons
Positive electrochemical active material be lithium battery manufacture in common used material, largely can directly be bought and be obtained by commercial sources
?.The type of conductive carbon can be using graphite, graphene, conductive black, carbon nanotube etc..In addition, by adjusting conductive carbon
The conductivity of the adjustable inorganic filler of coating content.
Other than the macromolecule matrix, conductive material and inorganic filler, the safety coatings that the present invention uses can also be wrapped
Containing other materials or component, such as promote coating and the binder as the adhesiveness between the substrate of collector etc..This field
Technical staff can select other auxiliary agents according to actual needs.
Since macromolecule matrix material itself used in safety coatings of the invention has good adhesiveness, in the present invention
Some embodiments in, it is (" basic that the safety coatings are substantially free of other binders other than the macromolecule matrix material
Without " indicate content≤3% ,≤1% or≤0.5%).In certain embodiments of the present invention, the safety coatings are basic
Without aqueous binders (such as CMC, polyacrylate, polycarbonate, polyethylene oxide, rubber, polyurethane, carboxymethyl cellulose
Plain sodium, polyacrylic acid, acrylonitrile multiple copolymer, gelatin, chitosan, sodium alginate, coupling agent, cyanoacrylate, polymerization
Cyclic ether derivative, hydroxy derivatives of cyclodextrin etc.).
In some embodiments, safety coatings of the invention can be substantially by the macromolecule matrix, conductive material
With inorganic filler form, i.e., without significant quantity (such as content≤3% ,≤1% or≤0.5%) other components.
It will be appreciated by those skilled in the art that: in safety coatings in above-mentioned different embodiments of the invention
Component selection, the various restrictions of constituent content and material physicochemical property parameter or preferred scope can in any combination, a combination thereof and
Obtained various embodiments still within the scope of the present invention, and are considered as a part of this disclosure content.
In the present invention, the coating thickness of the safety coatings be no more than 40 μm, preferably be not more than 25 μm, it is more excellent
Choosing is no more than 20 μm, 15 μm or 10 μm.The coating thickness of safety coatings be more than or equal to 1 μm, be preferably greater than or
Equal to 2 μm, more preferably greater than or equal to 3 μm.Thickness is too small, is not sufficient to ensure that safety coatings improve the effect of battery safety
Fruit；It is excessive, it will cause the internal resistance of cell and increase seriously, thus chemical property when influencing normal battery operation.
In electrode plates of the invention, safety coatings are coated on electrode current collecting body.For collector, can be used
The sheet metals such as material commonly used in the art, such as stainless steel, aluminium, copper, titanium or metal foil.
In electrode plates of the invention, electrode active material layers are provided with outside safety coatings.For anode pole piece, make
Use anode active material layer；For cathode, anode active material layer is used.
For the anode active material layer in the present invention can select it is well known in the art be suitable for lithium battery use it is various
Anode active material layer, is constituted and preparation method is well known in the art.It is living containing anode in the anode active material layer
Property substance, can be used that well known to a person skilled in the art the various positive electrode active materials for being used to prepare lithium ion secondary battery positive electrode
Matter, such as the positive active material are lithium-contained composite metal oxide, and specific material is, for example, LiCoO2、LiNiO2、LiMn2O4、
LiFePO4, one or more of lithium nickel cobalt manganese oxide (such as LiNi0.5Co0.2Mn0.3O2One of) and Li, Ni, Mn oxide
Or it is several.
When using nothing of the positive electrochemical active material (or its coating modification material) as the safety coatings of anode pole piece
When machine filler, the positive electrochemical active material in safety coatings and the positive-active used in anode active material layer
Substance can be the same or different.
For the anode active material layer in the present invention can select it is well known in the art be suitable for lithium battery use it is various
Anode active material layer, is constituted and preparation method is well known in the art.It is living containing cathode in the anode active material layer
Property substance, can be used that well known to a person skilled in the art the various negative electrode active materials for being used to prepare lithium ion secondary battery negative pole
The carbonaceous material of matter, for example, graphite (artificial graphite or natural graphite), conductive black, carbon fiber etc., such as Si, Sn,
The metals such as Ge, Bi, Sn, In or semi-metallic or its alloy, nitride containing lithium or lithium-containing oxides, lithium metal or lithium-aluminium alloy
Deng.
Disclosed herein as well is a kind of electrochemical appliance, which contains electrode plates according to the present invention.
The electrochemical appliance can be capacitor, one-shot battery or secondary cell.It such as can be lithium-ion capacitor, lithium ion one
Primary cell or lithium ion secondary battery.Other than having used electrode plates of the invention (anode pole piece and/or cathode pole piece), this
The construction and preparation method itself of a little electrochemical appliances are well known.Due to having used electrode plates of the invention, the electrification
Learning device can have improved safety and electrical property (such as cycle performance).And electrode plates of the invention are easily worked,
Therefore the manufacturing cost for having used the electrochemical appliance of electrode plates of the invention can be reduced.
Embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention is described in further detail.However, it should be understood that the embodiment of the present invention is of the invention just for the sake of explaining, and
It is non-in order to limit the present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.It is not infused in embodiment
Bright experiment condition uses normal condition, or the condition recommended using material supplier or equipment supplier.
1, preparation method
The preparation of 1.1 safety coatings
Using macromolecule matrix material, the conductive material, inorganic filler centainly matched, with n-methyl-2-pyrrolidone
(NMP) it is solvent, is coated on collector (plus plate current-collecting body aluminium foil or negative current collector copper foil) after mixing evenly, after drying
PTC layers (i.e. safety coatings).
The main material used in the safety coatings of each specific embodiment is as follows:
Macromolecule matrix material: PVDF, PVDC；
Conductive material (conductive agent): Super-P (TIMCAL company, Switzerland, abbreviation SP)；
Inorganic filler: aluminium oxide, LiFePO4 (abbreviation LFP), the LiFePO4 (being abbreviated as LFP/C) of coated modified carbon,
The lithium titanate of coated modified carbon (is abbreviated as Li4Ti5O12/ C), the cobalt acid lithium of cobalt acid lithium (abbreviation LCO), coated modified carbon (is write a Chinese character in simplified form
For LCO/C).
Material used above is that Lithium Battery Industry field is common and common used material, can be passed through by corresponding supplier
Commercial sources readily obtain.
The preparation of 1.2 anode pole pieces and cathode pole piece with safety coatings
Anode pole piece: 90wt% ternary material NCM811 (LiNi is used0.8Co0.1Mn0.1O2), 5wt%SP and 5wt%
PVDF is coated on the safety according to plus plate current-collecting body aluminium foil surface prepared by above-mentioned 1.1 using NMP as solvent after mixing evenly
On coating, layer as a positive electrode active material；It is cold-pressed after being dried at 85 DEG C, then trimming, cut-parts, slitting, then at 85 DEG C
It is dried 4 hours under vacuum condition, soldering polar ear, the anode of secondary battery pole piece (i.e. cathode sheet) met the requirements is made.
Cathode pole piece: in mass ratio by active material graphite, conductive agent Super-P, thickener CMC, bonding agent SBR
Anode slurry is made 96.5:1.0:1.0:1.5 being added to and being uniformly mixed in solvent deionized water；By anode slurry be coated on according to
It in the safety coatings of negative current collector copper foil surface prepared by above-mentioned 1.1, and is dried at 85 DEG C, then carries out trimming, cuts out
Piece, slitting, then dried 4 hours under 110 DEG C of vacuum conditions, the secondary battery negative pole pole piece met the requirements is made in soldering polar ear
(i.e. anode pole piece).
The preparation of 1.3 conventional cathode pole pieces and conventional anode pole piece
Conventional cathode pole piece: it is identical as the preparation method of 1.2 steps, in addition to plus plate current-collecting body aluminium foil surface is applied without safety
Layer.
Conventional anode pole piece: it is identical as the preparation method of 1.2 steps, in addition to negative current collector copper clad aluminum surface is without safety
Coating.
The preparation of 1.4 electrolyte
Ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) are mixed according to 3: 5: 2 volume ratios
EC/EMC/DEC mixed solvent is closed to obtain, then by sufficiently dry lithium salts LiPF6Being dissolved in the mixed solvent and obtaining concentration is 1M's
Solution is to get electrolyte.
The preparation of 1.5 batteries
Using 12 μm of polypropylene film as isolation film, anode pole piece, isolation film and cathode pole piece are folded in order, made
Isolation film, which is among anode pole piece and cathode pole piece, plays the role of isolation, is then wound into naked battery core.The vacuum at 75 DEG C
10h is toasted, (according to " preparations of 1.4 electrolyte " described preparation above) electrolyte is injected, by Vacuum Package, is stood for 24 hours,
0.05C is then dropped to 4.2V constant-voltage charge to electric current to 4.2V with the constant current charging of 0.1C later, then with 0.1C's
Constant current is discharged to 3.0V, is repeated 2 times charge and discharge, finally with the constant current charging of 0.1C to 3.8V, that is, completes secondary electricity
The preparation in pond.
2, the test of material property
It is unless otherwise specified, (mainly inorganic for each material for constituting safety coatings in each embodiment and comparative example
Filler) physical property, following methods are respectively adopted and are tested.
2.1 conductivity
Using the conductivity of RTS-4 type four-point probe test sample, measures 5 times and be averaged, unit S/m.
3, the performance test of battery
Using GBT31485-2015 " power accumulator safety requirements for electric vehicle and test method " to each embodiment and
The safety of the secondary cell of comparative example is assessed, and records test result.
3.1 lancing tests:
Secondary cell is completely charged to charge cutoff voltage with 1C electric current, then constant-voltage charge to electric current is down to 0.05C, stops filling
Electricity.WithHigh temperature resistant steel needle (cone angle of needle point be 45 °), with the speed of 25mm/s, from perpendicular to battery
The direction of pole plate is run through, and through position preferably close to the geometric center in pierced face, steel needle is stopped in the battery, and whether observation battery has
Burning, explosion phenomenon.
3.2 overcharge test:
Secondary cell is completely charged to charge cutoff voltage with 1C electric current, then constant-voltage charge to electric current is down to 0.05C, stops filling
Electricity.Then, stop charging with 1.5 times of 1C electric current constant current to end of charge voltage or after charging 1h.
The test of 3.3 cycle performances:
Cycle-index test condition are as follows: at 25 DEG C, secondary cell is subjected to 1C/1C loop test, charging/discharging voltage model
Enclose 2.8~4.2V, capacity attenuation to first discharge specific capacity 80% when stop test.
The test of 3.4PTC effect
Secondary cell is completely charged to charge cutoff voltage with 1C electric current, then constant-voltage charge to electric current is down to 0.05C, stops filling
Electricity is tested battery core D.C. resistance (4C current discharge 10s).Then battery core is placed in constant temperature 1h at 130 DEG C, tests direct current
Resistance calculates D.C. resistance growth rate；Then battery core is placed in constant temperature 2h at 130 DEG C, tests D.C. resistance, calculate D.C. resistance
Growth rate.
4, the performance test results
The protection effect (PTC effect) of 4.1 safety coatings and the influence to battery performance
In order to verify protection effect of the invention, with specific material and dosage listed in following table 1-1, according to " 1,
Method and steps described in preparation method " prepares corresponding safety coatings, anode pole piece, cathode pole piece and battery, then
It is tested according to the performance test of battery " 3, " part prescriptive procedure.In order to guarantee that data are accurate, every kind of battery prepares 4
(battery for lancing test prepares 10) and independent test, final testing result are averaged, shown in table 1-2 and table 1-3.
Wherein, conventional pole piece P and routine pole piece N are according to " preparations of 1.3 conventional cathode pole pieces and conventional anode pole piece " institute
State method preparation；Other pole pieces according to " 1.2 with safety coatings anode pole pieces and cathode pole piece preparations " the method with
In table prepared by the safety coatings material composition of defined.
Table 1-1: pole piece composition
Table 1-2: the performance test results of lithium ion battery
| Battery No. | Anode pole piece | Cathode pole piece | Lancing test |
| Battery 1 | Conventional pole piece P | Conventional pole piece N | 10 wholes do not pass through |
| Battery 2 | Compare pole piece CP | Conventional pole piece N | 2 pass through, and 8 do not pass through |
| Battery 3 | Pole piece 1 | Conventional pole piece N | 10 wholes pass through |
| Battery 4 | Pole piece 2 | Conventional pole piece N | 10 wholes pass through |
| Battery 5 | Conventional pole piece P | Pole piece 3 | 10 wholes pass through |
Table 1-3: the performance test results of lithium ion battery
Table 1-1, table 1-2 and table 1-3's statistics indicate that: electrode plates of the invention can substantially improve battery needle thorn peace
Full performance, and the addition of inorganic filler can be readily apparent that improve the D.C. resistance growth rate of battery under high temperature, so as to improve
The percent of pass of battery safety of acupuncture performance test.
The influence of constituent content in 4.2 safety coatings
For the influence of constituent content in further research safety coating, with specific material listed in following table 2-1
And dosage, corresponding safety coatings, anode pole piece, cathode pole are prepared according to method and steps described in " 1, preparation method "
Then piece and battery are tested according to the performance test of battery " 3, " part prescriptive procedure.In order to guarantee that data are accurate, every kind
Battery prepares 4 (battery for lancing test prepares 10) and independent test, final testing result are averaged, are summarized in
Table 2-2.
Table 2-1: pole piece composition
Table 2-2: the performance test results of lithium ion battery
| Battery | Anode | Cathode | Lancing test | Cycle life (cycle) |
| Battery 6 | Compare pole piece 2-1 | Conventional pole piece N | 5 do not pass through, and 5 pass through | 2502 |
| Battery 7 | Pole piece 2-2 | Conventional pole piece N | 10 wholes pass through | 2351 |
| Battery 8 | Pole piece 2-3 | Conventional pole piece N | 10 wholes pass through | 2205 |
| Battery 9 | Pole piece 2-4 | Conventional pole piece N | 10 wholes pass through | 2251 |
| Battery 10 | Pole piece 2-5 | Conventional pole piece N | 10 wholes pass through | 2000 |
| Battery 11 | Pole piece 2-6 | Conventional pole piece N | 10 wholes pass through | 2408 |
| Battery 12 | Pole piece 2-7 | Conventional pole piece N | 10 wholes pass through | 2707 |
| Battery 13 | Pole piece 2-8 | Conventional pole piece N | 10 wholes pass through | 2355 |
| Battery 14 | Pole piece 2-9 | Conventional pole piece N | 10 wholes pass through | 1800 |
| Battery 15 | Compare pole piece 2-10 | Conventional pole piece N | 4 do not pass through, and 6 pass through | 1715 |
Table 2-1 and table 2-2's statistics indicate that: (1) inorganic filler content is too low, then the PTC effect of safety coatings can not hundred
Hundred ground are divided to be played, therefore the security performance of battery cannot be fully improved；Inorganic filler content is excessively high, then polymer-based
Body content can be too low, then also not can guarantee safety coatings and normally play PTC effect；(2) internal resistance, polarization of the conductive material to battery
Be affected, therefore will affect the cycle life of battery, conductive material content is higher, then the internal resistance, polarization of battery are smaller, then
Cycle life is better.
Through experiments, it was found that the proper content range of each component of safety coatings is as follows:
The weight percent of macromolecule matrix is 35wt%-75wt%；
The weight percent of conductive material is 5wt%-25wt%；
The weight percent of inorganic filler is 10wt%-60wt%.
Influence of the 4.3 inorganic filler conductivities to battery performance
For influence of the material properties to pole piece and battery performance in further research safety coating, in following table 3-1
Listed specific material and dosage are prepared corresponding safety according to method and steps described in " 1, preparation method " and are applied
Then layer, anode pole piece, cathode pole piece and battery are tested according to the performance test of battery " 3, " part prescriptive procedure.For
Guarantee data are accurate, and every kind of battery prepares 4 (battery for lancing test prepares 10) and independent tests, final test
Results are averaged, is summarized in table 3-2.
Table 3-1: pole piece composition and material property
Table 3-2: the performance test results of lithium ion battery
| Battery | Anode | Cathode | Lancing test | Cycle life (cycle) |
| Battery 16 | Compare pole piece 2-11 | Conventional pole piece N | 10 wholes pass through | 2109 |
| Battery 17 | Pole piece 2-12 | Conventional pole piece N | 10 wholes pass through | 2204 |
| Battery 18 | Pole piece 2-13 | Conventional pole piece N | 10 wholes pass through | 2251 |
| Battery 19 | Pole piece 2-14 | Conventional pole piece N | 10 wholes pass through | 2294 |
| Battery 20 | Pole piece 2-15 | Conventional pole piece N | 10 wholes pass through | 2316 |
| Battery 21 | Pole piece 2-16 | Conventional pole piece N | 10 wholes pass through | 2407 |
Table 3-1 and table 3-2's statistics indicate that, the conductivity of inorganic filler has certain influence to the internal resistance of pole piece, battery,
Conductivity is higher, then internal resistance, polarization are smaller, then the cycle performance of battery is better.Further test discovery, when conductivityσ meets
10-3S/m≤σ≤102When S/m, battery security and electrical property are very good, and battery comprehensive performance is best.When filler conductance
Rate is less than 10-3S/m or be greater than 102When S/m, battery core security performance or electrical property are possible to be declined.
It will be appreciated by those skilled in the art that: it is only above the application for being illustrated safety coatings of the invention with lithium battery
Example, but safety coatings of the invention can be applied equally to other types of battery or electrochemical appliance, and still can be with
Obtain good technique effect of the invention.It will be appreciated by those skilled in the art that: it is of the invention in battery or electrochemical appliance
Safety coatings can be used for anode pole piece, cathode pole piece or simultaneously for anode pole piece and cathode pole piece, can play effective
Protective action.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula 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 the scope of the claims of the present 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 (11)
1. a kind of electrode plates, including collector, electrode active material layers and be set to collector and electrode active material layers it
Between safety coatings, the safety coatings include macromolecule matrix, conductive material and inorganic filler, the macromolecule matrix is poly-
Inclined fluoroolefins and/or gather inclined chloro-alkenes macromolecule matrix, based on the total weight of the safety coatings,
The weight percent of the macromolecule matrix is 35wt%-75wt%；
The weight percent of the conductive material is 5wt%-25wt%；
The weight percent of the inorganic filler is 10wt%-60wt%；
And the conductivityσ of the inorganic filler meets: 10-3S/m≤σ≤102S/m。
2. electrode plates according to claim 1, the macromolecule matrix is selected from Kynoar (PVDF), carboxyl acid modified
PVDF, acrylic acid modified PVDF, Vingon (PVDC), carboxyl acid modified PVDC, acrylic acid modified PVDC, PVDF
At least one of copolymer, PVDC copolymer.
3. electrode plates according to claim 1, the conductive material be selected from conducting carbon-based material, conductive metallic material and
At least one of conducting polymer materials,
Wherein conducting carbon-based material in conductive black, acetylene black, graphite, graphene, carbon nanotube, carbon nano-fiber extremely
Few one kind；
Conductive metallic material is selected from least one of Al powder, Ni powder, bronze；
Conducting polymer materials are selected from least one of conductive polythiophene, electric polypyrrole, electrically conductive polyaniline.
4. electrode plates according to claim 1, the inorganic filler is selected from metal oxide, nonmetal oxide, gold
Belong to conductive coated modified carbon, the conductive metal of at least one of carbide, non-metallic carbide, inorganic salts or above-mentioned material
At least one of coating modification or the material of conducting polymer coating modification.
5. electrode plates according to claim 1-4, wherein the weight percent of the macromolecule matrix is
50wt%-75wt%, the weight percent of the conductive material are 5wt%-15wt%, the weight percent of the inorganic filler
For 15wt%-45wt%.
6. electrode plates according to claim 1-5, the thickness H of the safety coatings is 1 μm≤H≤20 μm,
Preferably 3 μm≤H≤10 μm.
7. electrode plates according to claim 1-6, the electrode plates are anode pole piece.
8. electrode plates according to claim 7, the inorganic filler is selected from cobalt acid lithium, the conduction of conductive coated modified carbon
The nickel manganese cobalt acid lithium of coated modified carbon, the nickel manganese lithium aluminate of conductive coated modified carbon, conductive coated modified carbon LiFePO4, lead
The phosphoric acid vanadium lithium of electrical carbon coating modification, the cobalt phosphate lithium of conductive coated modified carbon, the lithium manganese phosphate of conductive coated modified carbon, conduction
The ferric metasilicate lithium of coated modified carbon, the vanadium lithium silicate of conductive coated modified carbon, the cobaltous silicate lithium of conductive coated modified carbon, conductive carbon
The manganese silicate of lithium of coating modification, the lithium manganate having spinel structure of conductive coated modified carbon, conductive coated modified carbon spinel-type nickel
At least one of LiMn2O4, lithium titanate of conductive coated modified carbon.
9. a kind of electrochemical appliance, including anode pole piece and cathode pole piece, wherein anode pole piece and/or cathode pole piece are wanted for right
1 to 6 described in any item electrode plates are sought, the electrochemical appliance is capacitor, one-shot battery or secondary cell.
10. a kind of electrode plates safety coatings, the safety coatings are comprising gathering inclined fluoroolefins and/or gathering inclined chloro-alkenes macromolecule
Matrix, conductive material and inorganic filler, the macromolecule matrix are to gather inclined fluoroolefins and/or gather inclined chloro-alkenes macromolecule matrix,
Based on the total weight of the safety coatings,
The weight percent of the macromolecule matrix is 35wt%-75wt%；
The weight percent of the conductive material is 5wt%-25wt%；
The weight percent of the inorganic filler is 10wt%-60wt%；
And the conductivityσ of the inorganic filler meets: 10-3S/m≤σ≤102S/m。
11. electrode plates safety coatings according to claim 10, wherein the weight percent of the macromolecule matrix
For 50wt%-75wt%, the weight percent of the conductive material is 5wt%-15wt%, the weight percent of the inorganic filler
Than for 15wt%-45wt%.
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