CN108539252A - A kind of high security lithium ion battery - Google Patents
A kind of high security lithium ion battery Download PDFInfo
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- CN108539252A CN108539252A CN201710126051.2A CN201710126051A CN108539252A CN 108539252 A CN108539252 A CN 108539252A CN 201710126051 A CN201710126051 A CN 201710126051A CN 108539252 A CN108539252 A CN 108539252A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 136
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- 239000011247 coating layer Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000013543 active substance Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- 239000012530 fluid Substances 0.000 description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- -1 NMP N-Methyl pyrrolidones Chemical class 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
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Classifications
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- 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
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
This application discloses a kind of high security lithium ion batteries.The electronic conductivity of the electrode active material coating of the battery is in be distributed from high to low from collection liquid surface to coating outer surface.The distribution realizes that the slurry of each layer choosing heterogeneity controls the distribution of conductivity by changing the content of conductive agent and bonding agent contained in slurry by multi-layer coated mode.The distribution of conductivity can reduce short circuit current, improve safety；Meanwhile the distribution of conductivity is similar to the distribution of normal charging and discharging currents, in side of the positive electrode, conductive agent utilization rate improves, and can have more spaces to leave electrode active material for, to make energy density improve.
Description
Technical field
The application belongs to field of batteries, it particularly relates to there is the lithium ion battery of greater security when a kind of internal short-circuit.
Background technology
Lithium ion battery has extended cycle life using it, energy density is high and the advantage of environmental protection by wide selection as consumer
The power supply of electronic product and the power source of new-energy automobile.But there is also the security risks that can not be ignored for lithium ion battery.According to report
Road has a lot of mobile phones that the accident of combustion explosion occurs because lithium ion battery is bad, is related to the renowned companies such as Samsung, apple, some
Event results in recalling for product；The example that combustion explosion occurs for lithium ion battery electric vehicle also has many reports, is related to wrapping
Include the well-known electric vehicle enterprise such as BYD, tesla.
In the security risk that lithium ion battery faces, main and most serious is exactly thermal runaway.Thermal runaway is sent out
Exhibition is closely related with internal short-circuit, if internal short-circuit electric current is big, short dot temperature increases, and internal short-circuit itself can cause thermal runaway；
In the thermal runaway that other reasons cause, internal short-circuit is also a crucial growth encourage factor, such as when overcharging initiation thermal runaway, generation
Initial stage temperature increases, once reaching diaphragm breakup temperature, then will produce internal short-circuit, once internal short-circuit occurs, electric energy then may be
Nearby quick release, the heat of generation can promote battery diaphragm to accelerate to shrink thawing to internal short-circuit point, and the thawing of diaphragm is destroyed into one
Step, which increases short-circuit area, reduces the resistance of short dot, to accelerate the release of electric energy, aggravates thermal runaway.
The situation that internal short-circuit occurs can be divided into 2 kinds, and a kind of situation is that lithium ion battery meets with extraneous strong abuse, such as
It seriously overcharges, sharp pounding is hit, severe crush deformation, is burnt or is pierced through by foreign matter；Another situation is battery normal
In working cycles, under relatively mild use condition, due to collection caused by Li dendrite, the deposition of iron, metal burr, pulsating stress
The reasons such as fluid cracking generate the micro-short circuit of contact point area very little under the perturbation action of temperature and pressure.
Internal short-circuit needs to avoid as far as possible certainly.Well known technology is by reducing the percent thermal shrinkage of diaphragm, strictly controlling work
Skill avoids the generation of metal burr, ensures that cathode is enough and reduce rate of charge in low temperature to avoid the side such as generation of Li dendrite
Formula generates the probability of internal short-circuit to reduce.It is well known in order to avoid internal short-circuit caused by the thermal contraction of battery diaphragm at high temperature
Technology is to improve the high temperature safety of battery making one layer of heat-resisting ceramics layer between diaphragm and electrode.Common side
Formula is that ceramic powders are attached to the both sides of diaphragm by way of coating, diaphragm processed in this way be referred to as ceramics coating every
Film or CCM（Ceramic Coated Membrane）.Despite the use of above-mentioned well known technology, current technology level there is no
Method by the probability that internal short-circuit and thermal runaway occur be reduced to one it is negligible below horizontal.
After internal short-circuit especially micro-short circuit occurs, not necessarily lead to thermal runaway, the internal short-circuit of non-thermal runaway type is in macroscopic view
On show as the self-discharge rate of battery and rise, in battery pack, the uneven aggravation that is presented as between battery cell.Internal short-circuit is such as
Fruit is not avoided that we then wish that it is presented as that mild self-discharge rate rises, rather than thermal runaway.If short in giving
Under the situation of road, the electric current of internal short-circuit can be reduced, then can avoid or reduce the risk of thermal runaway.
Internal short-circuit safety is related to the multiplying power property of battery, forthright again and with battery pole piece the electronic conductivity of battery
It is related.In well known technology, in order to reduce the risk of thermal runaway after internal short-circuit occurs, generally require to reduce the forthright again of battery
It can, that is to say, that also reduced while reducing internal short-circuit electric current and normally allow charging and discharging currents.However no matter for disappearing
Take electron-like or power applications, the high rate capability of lithium ion battery is often again a key index.High power charging-discharging
It is required that the electronic conductivity of electrode slice active material coating is high good in lithium ion cell electrode group, however from a safety viewpoint
It sees, the electrode slice coating of highly electron conductive, it is meant that big internal short-circuit electric current.Well known technology is difficult to solve this contradiction.
In addition, high electronic conductivity, pole piece especially not strong to the electric conductivity of electrode active material, need to increase in electrode coating
The content of conductive agent, however means that the content of active material is reduced, to reduce the energy density of lithium ion battery.
The electronic conductivity of electrodes of lithium-ion batteries active material coating, by pole piece active material layer ingredient, the uniformity, and
The influence of densification etc..It is generally stirred using several hours high intensity so as to which material is homogenized in lithium galvanic process.Because densification is
The key factor of volume energy density is influenced, so in the mechanical performance for not damaging pole piece, and can ensure that electrolyte infiltrates
Under the premise of amount, densification should improve as far as possible.Under conditions of the determining uniformity and densification, the electronic conductivity of coating takes
Certainly in component ratio.The ingredient of pole coating slurry generally comprises electrode active material, binder, conductive agent and solvent.It is molten
Agent will volatilize away during drying, last to be only left remaining solid matter.The content for increasing conductive agent, can improve
The electronic conductivity of pole piece coating increases the content of binder, will reduce its electronic conductivity, because binder is usually to insulate
Material.
In well known technology, on a current collector by electrode slurry coating, then pole is obtained by dry, roll-in and cutting
Piece.The electronic conductivity of pole piece top electrode active material coating is basically uniform.Although due to the fluctuation of technological parameter, institute
Stating electronic conductivity can be varied from, or due to natural, such as if the rate of drying of electrode slurry is slower, electrode
Slight sedimentation can occur for slurry, cause, but the influence of these fluctuating factors slightly higher in coating surface binder content after drying
It is smaller, and in well known technology, there is no the electronic conductivities for carrying out purposive control coating using these influence factors to press
Change according to certain rule.
However uniform conductivity in electrode slice active material coating, from internal short-circuit safety and battery energy density
From the perspective of, it is not most rational situation.In a charge cycle or a discharge cycle, from electrode current collecting body surface
Start, average electron current density continuously decreases, and when arriving electrode coating outer surface, average current density is close to zero.Its
If reason is it will be understood that our electrode active material layers thickness is 100 microns after roll-in, it is contemplated that between in the coating
Namely thick 50 microns of place, there are one virtual interfaces, then from interface to the charge and discharge on electrode active material layers surface
Capacitance is the half of the electrode slice total capacity, thus on this virtual interface, mean charging current density or is averagely put
Electric current density, with regard to the half of the corresponding current density of collection liquid surface.It can think roughly, be put in a charge cycle or one
In the electric period, electron current density is from collection liquid surface to coating outer surface, from maximum value linear reduction to being zero.Certainly in reality
In the case of border, the distribution of electron current density is also influenced by multiplying power, mass transport process etc., and linear change can't be strictly pressed,
But this reduction trend from inside to outside is constant.Due to from collection liquid surface to electrode active material coating surface, electronics
Current density is to be reduced to zero from maximum, so in entire active material coating, being evenly distributed for conductive agent is not just
One optimal option.Because low far from afflux volume current density close to outer layer, conductive agent is not fully utilized, and ties up instead
Space reduces the energy density of electrode slice.More seriously, under conditions of normal current is distributed, work cannot be given full play to
Outer layer conductive agent can play the effect for improving internal short-circuit electric current when internal short-circuit occurs for battery, and thermal runaway is made to be easier to send out
It is raw.Because when internal short-circuit occurs, distribution and the normal condition trend of internal short-circuit point-like electron electric current are on the contrary, close to pole piece
The position of short dot, electron current density bigger.
In this way, using well known technology, make the equally distributed lithium-ion electric of the electronic conductivity of electrode slice active material layer
Pond not only wastes space, but also has larger thermal runaway risk in internal short-circuit..
Invention content
To overcome the above-mentioned deficiency of the prior art, this application provides a kind of high security lithium ion batteries.
The purpose of the application is：So that short circuit current when generation internal short-circuit is reduced, causes to reduce internal short-circuit
The probability of thermal runaway；The another object of the application is：The component distributing for optimizing electrode slice coating, improves the energy of lithium ion battery
Metric density.
Technical solution is used by the application solves its technical problem：
Make the electronic conductivity of electrode slice active material coating from collection liquid surface to coating outer surface along perpendicular to collector
It is distributed by rule from high to low on normal to a surface direction.
Optionally, the electronic conductivity that electrode slice active material coating is adjusted by adjusting the ratio of conductive agent, makes close
The position of collector, conductive agent content is high, and close to the position of diaphragm, conductive agent content is low, can obtain expected electronic conductance
Rate is distributed.Optionally, the electronic conductivity of electrode slice active material coating, positive-active are adjusted by adjusting the ratio of binder
The common bonding agent Kynoar of material（PVDF）And the common bonding agent butadiene-styrene rubber of negative electrode active material（SBR）All it is
Insulating materials makes close to the position of collector, and binder content is low, and close to the position of diaphragm, binder content is high, can obtain
Expected electronic conductivity distribution.
For positive plate, since the electron conduction of positive electrode active materials is not generally strong, it is preferable to use adjustment conductive agent ratio
The mode of example is distributed to adjust its electronic conductivity, and the space got off is saved from optimization conductive agent distribution mode for accommodating more
More positive electrode active materials, to improve energy density.For negative plate, it is preferable to use the mode of adjustment binder ratio adjusts its electricity
Electron conductivity is distributed, because cathode generally uses graphite material, its own electron conduction is good, even if without conductive agent, coating
Electronic conductivity it is also quite high.
The advantageous effect of the application is：
It due to the electronic conductivity of electrode slice active material coating, is continuously decreased from internal layer to outer layer, so internal short-circuit occurs
When, short circuit current reduces, and is not susceptible to thermal runaway.
Internal short-circuit occurs but does not lead to thermal runaway, just gives the time of battery management system abundance, can detect and put certainly
Phenomena such as electric, alarms and takes safety measures so as to provide.
Electronic conductivity and current density are more identical along the distribution of active material layer thickness direction, the utilization of positive conductive agent
Rate higher, the conductive agent content close to surface layer can reduce, and to save out space, make the energy density of battery can be with higher.
Description of the drawings
The application is further illustrated with reference to the accompanying drawings and examples, wherein：
Fig. 1 show lithium ion cell electrode group partial structural diagram；
Fig. 2 show lithium ion cell positive regular picture electric current flow field schematic diagram；
Fig. 3 show lithium ion cell positive normal charging current flow field schematic diagram；
Fig. 4 show lithium ion battery and positive electrode current flow field schematic diagram when internal short-circuit occurs；
Fig. 5 show the multi-layer coated electrode slice structural schematic diagram of lithium ion cell positive.
Reference numeral：
Plus plate current-collecting body 1, anode electrode coating layer of active substance 2, positive internal layer electrode coating layer of active substance 2A, positive outer layer
Electrode active material coating 2B, side of the positive electrode diaphragm heat resistant ceramic coatings 3, membrane for polymer matrix 4, negative side diaphragm are heat-resisting
Ceramic coating 5,3,4 and 5 collectively constitute ceramics apply cloth diaphragm, negative electrode coating layer of active substance 6, negative current collector 7, just
Pole electrode active material coating surface internal short-circuit point 8.
Specific implementation mode
To make technical problem solved by the invention, technical solution and advantage be more clearly understood, below in conjunction with
The present invention is further described in detail for embodiment and attached drawing.It should be appreciated that specific embodiment described herein is only
For explaining the present invention, it is not intended to limit the present invention.
The method is conventional method unless otherwise instructed.The material unless otherwise instructed, can be from open business
Approach is commercially available.
Fig. 1 show a kind of typical lithium ion cell electrode group partial structural diagram.No matter lithium ion battery is to adopt
With takeup type or stacked technique, partial structurtes are coated with by the ceramics to insulate between anode and cathode as shown in Figure 1
Diaphragm separates, and in order to reduce the shrinking percentage of membrane for polymer matrix 4 at high temperature, improves safety, general polymerization object diaphragm base
4 both sides of body can also coat the heat-resisting ceramics layer 3 and 5 that insulate.For brevity, the electricity of collector single side is only depicted in Fig. 1
Pole active material coating, in virtual electrode group, all active material coating in collector two sides spatially forms the knot of repeatability
Structure.In finished battery, electrode group can be adsorbed after fluid injection chemical conversion full of electrolyte, electrolyte can be full of ceramics apply cloth diaphragm,
Hole in anode electrode coating layer of active substance 2 and negative electrode coating layer of active substance 6.In normal charge and discharge process, anode
Electrode active material coating 2 will produce electronic current, close to coating surface layer, that is, be closer to the active material institute of diaphragm position
The electronic current of generation must be flowed to the direction of collector, converged during flowing produced by internal layer active material
Electronic current, so, electron current density is constantly accumulated from coating outer surface to collection liquid surface, increases from zero to maximum
Then value imports plus plate current-collecting body 1 and eventually flows to the positive terminal of battery.Plus plate current-collecting body is generally more than ten micron
Thick aluminium foil, resistance is relatively low, can be considered as equipotentiality body.Fig. 2 show the signal of lithium ion cell positive regular picture electric current flow field
Figure.Fig. 3 show lithium ion cell positive normal charging current flow field schematic diagram.Notice that arrow show electric current in Fig. 2 and Fig. 3
Direction, since an electron is negatively charged, direction is opposite shown in the flow direction of electronics and arrow.It is noted that it is discussed herein,
Electric current in Fig. 2, Fig. 3 and Fig. 4 is electronic current, rather than ionic current, ionic current flow in the electrolytic solution depend on from
The parameters such as electron conductivity and porosity.
Electronic current hangs down in electrode active material coating when charge and discharge normal due to lithium ion battery shown in Fig. 2 and Fig. 3
Directly in the characteristic distributions on collector direction, so the equally distributed electrode coating of conductive agent, the conductive agent of outer layer cannot get
It makes full use of.It is not a kind of optimization for this lithium ion battery for doing everything possible to improve battery energy density for needs
Structure.However problem is more than that, the outer layer conductive agent being not fully utilized, when internal short-circuit occurs for battery, exactly
The evil idea of key is played.Fig. 4 show positive electrode current flow field schematic diagram when internal short-circuit occurs for lithium ion battery, anode in figure
Electrode active material coating surface short dot 8 is for some reason that for example the Li dendrite to grow out from cathode punctures diaphragm,
Cause the point that the position of internal short-circuit occurs.Significantly, since short dot seems bigger in the reason of engineer's scale figure,
But the single side typical thickness of positive electrode active materials coating is about 50 microns actually after roll-in, short dot size as shown in the figure and
Positive electrode active materials coating layer thickness is close, so size and little.If it is internal short-circuit caused by Li dendrite, since lithium metal exists
It is zero potential point standard in lithium battery system, it is possible to think that the current potential of positive coating surface short dot is reduced to zero.Such as
Fruit is metal burr anode is connected to cathode caused by internal short-circuit, due in well known lithium power technology, negative electrode active material
The graphite of generally high electron conduction, so the electronic conductivity of cathode coating is much larger than positive coating, ohm after short circuit
Voltage drop occurs mainly in positive coating, and the current potential of lithium intercalated graphite still can be approximately considered interior short close to lithium metal
The current potential of positive coating surface short dot is reduced to be approximately equal to zero behind road.There is the case where charging and discharging currents if it is in battery
Under, internal short-circuit electric current can be superimposed upon on normal charging and discharging currents, since the general internal resistance of lithium ion battery is relatively low, there is charge and discharge
When electric current, if not multiplying power it is very high if, the variation of normal electrode potential also less greatly, so in normal charge and discharge
Or the space distribution modes of internal short-circuit electric current approach in the case of two kinds of open-circuit condition.The numerical values recited load-bearing of certain internal short-circuit electric current
Electricity condition is affected, and state-of-charge is higher, and internal short-circuit electric current is bigger, and the internal short-circuit under overcharging state is particularly hazardous.For letter
For the sake of list, state shown in Fig. 4 is battery in the case that namely charging and discharging currents are zero under outer open circuit state, hair
Current distribution when raw internal short-circuit.Since the current potential of short dot 8 is zero, electric current will flow to short dot, it should be noted that be marked in figure
Be current direction, the flow direction of actual carrier electrons is just with current direction on the contrary, the flow direction of electric current is abided by
Two kinds of mechanism are followed, the first is that the conductive network being made up of the conductive agent of positive electrode active materials coat inside flows directly into short circuit
Point 8, second is as regular picture, and electric current first flows to collector, and being then transported to short dot 8 again by collector exists
Near subpoint on plus plate current-collecting body, short circuit is flowed to by the active material coating between collector and short dot 8 again later
Point.Since the electronic conductivity of collector is far above positive electrode active materials coating, so the positive-active material near short dot 8
In the bed of material, electric current follows first way and flows directly into short dot 8, in from the anode active material layer remotely of short dot 8,
Electric current will be flowed by the second way.If Fig. 4 is shown, the positive-active material of the current density of short circuit current near short dot 8
The surface of material coating reaches maximum value, so the highly electron conductive at this will lead to big short circuit current, it is unfavorable to safety.Make
The electronic conductivity of anode electrode coating layer of active substance 2 is constantly reduced from collection liquid surface to outermost layer, is that can improve battery
Energy density, can also improve the preferred embodiment of its safety.Current distribution in negative electrode coating layer of active substance is normal
It is also similar with anode under charge and discharge or short-circuit conditions.However since the conductivity of negative electrode active material graphite is higher, so generally
In the case of short circuit when voltage drop caused by the electronic conductance of cathode again smaller than anode, by adjusting the conductance of cathode coating
Rate distribution is also not so good as adjustment side of the positive electrode significant effect to improve safety.
The application adjusts the distribution of its electronic conductivity by adjusting the ingredient of electrode active material coating.Due to anode
The general electric conductivity of active material is weaker, and anode electrode coating electronic conductivity is mainly provided by conductive agent, and the content of conductive agent is high
Then conductivity is high, and the low then conductivity of content of conductive agent is low, and anode electrode coating electronic conductivity is also influenced by bonding agent, often
Binder such as Kynoar（PVDF）It is insulator, then conductivity is low for the content height of bonding agent, and the content of binder is low
Then conductivity is high.Optionally, make the coating inner layer conductive agent content close to plus plate current-collecting body high, make the painting far from plus plate current-collecting body
Layer outer layer conductive agent content is low, to make the distribution optimization of conductivity.Optionally, electricity is adjusted by adjusting the content of binder
Conductance, but it is noted that the content of binder cannot be too low, the mechanical property of electrode coating can otherwise deteriorated, leads to electrode
The deleterious aspects such as piece picking.For cathode, active material is frequently with graphite.Negative electrode coating also contains a small amount of conduction
Agent, the purpose of cathode conductive agent are to disengage to reduce so as to cause actual capacity between avoiding graphite active material granule.By
It is good in the electron conduction of graphite material, it is difficult to by reducing the content of conductive agent, the electronic conductivity on negative plate surface to be made to drop
As low as desired value.The common binder of cathode such as butadiene-styrene rubber is also insulator.Optionally, containing by adjusting negative electrode binder
It measures to adjust cathode conductivity, increases the content of negative electrode binder on the surface layer of electrode coating, to reduce its conductivity.It needs to note
Meaning, the increase of negative electrode adhesive coating content are unfavorable to energy density index.The application preferably only adjusts positive plate coating
The spatial distribution of electronic conductivity to improve internal short-circuit safety, while can also improve the energy density of lithium ion battery.It is optional
, if internally short circuit safety requirement is high, the electronic conductivity of positive plate coating and negative plate coating is adjusted simultaneously
Spatial distribution.
It is needed through certain coating method in electricity after the component distributing target that electrode active material coating is determined
The coating of the object construction is formed on the collector of pole.In well known technology, the coating to affluxion body in lithium ion batteries is general first
Slurry is made in electrode active material, conductive agent, binder and solvent together mixing, collection is then applied to using extrusion coated
On fluid.From with the prior art compatible angle as much as possible, extrusion coated can be selected to the implementation of the application.Due at this
In application, in the coating of collector one side, the content of different location conductive agent or binder is not equal, so to collection
Often needing on one side for fluid is multi-layer coated.The optional coating machine using the prior art uses heterogeneity to the single side of collector
One layer every time of slurry, repeatedly be coated with；Also optional to improve existing coating machine, using the coating head of Multiple level, each gap is squeezed
Extrude heterogeneity slurry, while on the single side of collector coated with multiple layer heterogeneity wet coating, then simultaneously dry
Winding, then it is coated with the another side of collector in the same fashion.It can be repeatedly coated with and be led to avoid single layer using Multiple level extrusion coated
Cause it is multiple reload repeatedly to coater head volume from coating tail, to improve efficiency.
Optionally, coating of the application for electrode current collecting body is coated with using slope flow liquid bridge.Slope flow liquid bridge coating is film
Common coating method well known to one kind in production.Masking liquid enters the cavity of extrusion nozzle, forms uniform liquid film through choked flow gap, edge is inclined
Then slope flowing is transferred on matrix to be coated by liquid bridge, to achieve the purpose that coating, the coating of slope flow liquid bridge are suitble to
The small electrode activity thing material of grain size, can be rapidly coating with single multilayer.
The conductivity on electrode active material coating surface layer is more important to safety.As seen from Figure 4, electric current flow field is short
The mode of the radial convergence of waypoint, so the conductivity of pole piece coating outermost thin layer most closes the influence of the size of short circuit current
Key, preferred mode should be the conductivity of coating outermost thin layer to be reduced as possible, while in order to avoid being made to normal charge and discharge
The thickness of the pressure drop of Cheng Tai great, outermost low conductivity layer also wants very little.So the coating number of plies is more, the distribution of conductivity is got over
It provides easy access to optimize.
Rational coating method makes every effort to the distribution optimization for making conductivity, but also to be restricted by specific technological ability.Often
Extrusion coated technique has certain coat window, be exactly in the case of viscosity and certain coating line speeds, coating it is wet
It if thickness is too thin, will cause be coated with, hollow equal coating defects occur.Therefore use extrusion coated, collector it is each
Preferred 2 to 5 layers of the coating in face.Therefore, in order to obtain the low conductivity thin layer on electrode active material coating surface layer, optionally, with squeeze
The mode of extrusion cloth first carry out it is multi-layer coated reach the coating weight close to final surface density, then again be suitble to thin-layer coating work
Skill supplies remaining outer layer surface density coating weight.
Optionally, the application uses the mode of intaglio printing to be coated with one or more layers close to supply the remaining outer layer surface
Spend coating weight.Intaglio printing is suitable for relatively thin coating, can accomplish that thickness is several microns.Optionally, the application uses silk
The mode of wire mark brush is coated with one or more layers to supply the remaining outer layer surface density coating weight.Silk-screen printing be also suitable for compared with
Thin coating, and be a kind of highly developed technique.Optionally, the application is coated with one or more layers by the way of ion plating
To supply the remaining outer layer surface density coating weight.Optionally, the application is coated with one layer or more by the way of magnetron sputtering
Layer is to supply the remaining outer layer surface density coating weight.Magnetron sputtering is the semiconductor technology of maturation, is easily able to precision
Control, the disadvantage is that speed is slower when being coated with big thickness, the thickness for being used to be coated with 1 to 10 microns of outermost layer in this application is can
Capable.Positive electrode active materials can be selected in magnetron sputtering process and 2 kinds of targets are made in conductive agent tabletting, followed both in sputtering process
Ring replaces, by controlling its time accounting i.e. controllable ratio respectively in the coating.
The application is further described below by embodiment.
Embodiment 1
Fig. 5 show the multi-layer coated electrode slice structural schematic diagram of lithium ion cell positive.It is coated with successively just on plus plate current-collecting body 1
Pole internal layer electrode active material sub-layer 2A and positive outer electrode active material sub-layer 2B.The key of sub-layer 2A and sub-layer 2B
Difference lies in the differences of the different and resulting sub-layer electronic conductivities of conductive agent content.
Positive list of ingredients A
| Cobalt acid lithium | sp | ks-6 | PVDF | NMP |
| 1000±0.5 | 18±0.1 | 12±0.1 | 21±0.1 | 450 |
Positive list of ingredients B
| Cobalt acid lithium | sp | ks-6 | PVDF | NMP |
| 1015±0.5 | 9±0.1 | 6±0.1 | 21±0.1 | 450 |
In above-mentioned two table：Sp conductive blacks, ks-6 electrically conductive graphites, PVDF Kynoar（Molecular weight need to be more than 1,000,000）,
NMP N-Methyl pyrrolidones.
Numerical value is weight ratio in table, and unit is a parts by weight.By listed object in positive list of ingredients A and positive list of ingredients B
Material respectively through dehydration, mix with power mixer 12 hours, colloid mill, removal magnetisable material and use extrusion coating machine after being sieved
It is coated.The dosage of solvent can as one sees fit increase and decrease according to viscosity measurement, so that slurry obtains required viscosity in favor of applying
Cloth.Dispensing and homogenate are technologies known in the industry, this place does not repeat its all details.Plus plate current-collecting body 1 uses 12 μ m-thick aluminium foils,
Aluminium foil surface density use scope：32±3g/m2.The double-deck coating is all carried out per one side to aluminium foil.The coating of first sub-layer is using just
List of ingredients A corresponding slurries in pole form sub-layer 2A, and the coating of the second sub-layer forms sub-layer using the corresponding slurries of positive list of ingredients B
2B.Coating thickness is according to actual measurement dressing Auto-regulating System of Density of Heavy Medium, the surface density examination criteria after sub-layer drying：Single-surface single-layer dressing density：
110±1.5g/m2, single-surface double-layer layer dressing density：220±3g/m2, two-sided double-deck dressing density：440±6g/m2.Coating machine
Using X-ray thickness gauge monitor coating surface density and at any time manual adjustment with ensure coating consistency.Coating processes are bottom
It is exactly that 2A layers of leading extrusion coated are then dry, the material volume wound after drying places back in squeezing for 2B layers of coater head progress
Extrusion cloth.When applying 2B layers, NMP is sprayed on the 2A layers dried before extrusion coated head by ten alignment atomizers
Solvent, effect are to soak dried sub-layer surface layer, improve the infiltration between fresh wet coating and preceding primary coating sub-layer
Property, avoid sub-layer caused by not infiltrated due to surface is hollow from waiting coating qualities problem.In the present embodiment, the coating of cathode is still pressed
According to well known technology single layer is coated with per one side for upper in copper current collector.Coating complete after, through vacuum bakeout, roll-in, slitting,
It weighs, welding electrode ear, rubberizing paper, winding, lithium is made in the processes such as envelope, vacuum drying, fluid injection, aging, chemical conversion, two envelopes and partial volume in advance
Ion battery final products.Technology known in the industry involved by each process, is not added with repeats herein.
Embodiment 2
The present embodiment difference from Example 1 is, in addition to anode, negative current collector 7 also does two layers of coating per one side.With
Anode is similar, and the electronic conductivity of two sublayers is also different, and the inner electron conductivity close to negative current collector 7 is higher, and outer
Layer electronic conductivity is then relatively low.Since the electronic conductivity of graphite itself is high, so by adjusting the mode tune of binder content
The electronic conductivity of whole negative electrode active material coating is distributed.
Cathode blending Table A
| Artificial graphite | CMC powder | sp | SBR | NMP+ deionized waters |
| 1000±0.5 | 15.8±0.1 | 10 | 54±0.1 | 50+1009 |
Cathode blending table B
| Artificial graphite | CMC powder | sp | SBR | NMP+ deionized waters |
| 970±0.5 | 15.8±0.1 | 10 | 85±0.1 | 50+1009 |
In above-mentioned two table：CMC sodium carboxymethylcelluloses, SBR butadiene-styrene rubber, sp conductive blacks, NMP N- crassitudes
Ketone.
Numerical value is weight ratio in table, and unit is a parts by weight.By listed object in cathode blending Table A and cathode blending table B
Material mixes 12 hours with power mixer, colloid mill and is coated with extrusion coating machine after being sieved.Negative current collector 7 makes
With 9 μm of copper foils, copper foil surface density use scope：65±5g/m2.The double-deck coating is all carried out per one side to copper foil.The use of solvent
Amount can as one sees fit increase and decrease according to viscosity measurement, so that slurry obtains required viscosity in favor of coating.Dispensing and homogenate are industry
Interior well known technology, this place does not repeat its all details.Internal layer coating uses the corresponding slurry of cathode blending Table A, outer layer coating
Use the corresponding slurries of cathode blending table B.According to dressing Auto-regulating System of Density of Heavy Medium is surveyed, the surface density after coated and dried detects coating thickness
Standard：Single-surface single-layer dressing density：53+1g/m2, single-surface double-layer layer dressing density：106+2g/m2, two-sided double-deck dressing density：
212+4g/m2.Coating machine monitors coating surface density using beta thickness gauge and manual adjustment is consistent to ensure to be coated at any time
Property.Coating is then dry in advance for internal layer for coating processes, and it is outer that the material volume wound after drying places back in coater head progress
The extrusion coated of layer.When applying outer layer, before extrusion coated head by ten alignment atomizers on the internal layer dried
Deionized water is sprayed, effect is to soak dried coating surface layer, improve between fresh wet coating and preceding primary coating
Wellability avoids coating caused by not infiltrated due to surface is hollow from waiting coating qualities problem.After positive and negative anodes coating is respectively completed,
Through vacuum bakeout, roll-in, slitting, weigh, welding electrode ear, rubberizing paper, winding, in advance envelope, vacuum drying, fluid injection, aging, chemical conversion, two
Lithium ion battery final products are made in the processes such as envelope and partial volume.Technology known in the industry involved by each process, is not added with superfluous herein
It states.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also be to above-mentioned embodiment party
Formula carries out change, combination and modification appropriate.Therefore, the application is not limited to specific embodiment party disclosed and described above
Formula should also be as falling into the protection domain of claims hereof to some modifications and changes of the application.In addition, although originally
Some specific terms are used in application, these terms are merely for convenience of description, is not constituted to the application any
Limitation.
Claims (10)
1. a kind of lithium ion battery includes shell and the electrode group being sealed in shell and electrolyte, the electrode group includes two kinds
Electrode active material coating, the positive electrode active materials coating being respectively attached on plus plate current-collecting body and and be attached to negative pole currect collecting
Negative electrode active material coating on body, which is characterized in that at least one of described two electrode active material coatings are from collection
Flow surface to coating outer surface along in the normal direction of collection liquid surface electronic conductivity by being distributed from high to low.
2. lithium ion battery according to claim 1, which is characterized in that by changing in the electrode active material coating
Mass ratio shared by conductive agent or bonding agent makes the mass ratio in the normal direction by from high to low, or from low to high
Distribution is distributed with obtaining the electronic conductivity.
3. lithium ion battery according to claim 1, which is characterized in that the electrode active material coating is by least two layers
Sub-layer forms, and the ingredient of each sub-layer is different, and inside the sub-layer, electronic conductivity is uniformly distributed, between adjacent sublayers,
Electronic conductivity stepped change, the sub-layer electronic conductivity closer to collector is higher, the sub-layer electronic conductance closer to surface layer
Rate is lower.
4. lithium ion battery according to claim 3, which is characterized in that each sub-layer of the electrode active material coating
It is coated on collector with the mode of extrusion coated, adjacent another sub-layer is coated after dry.
5. lithium ion battery according to claim 3, which is characterized in that multiple sub-layers of the electrode active material coating
It once completes to be coated with the mode of Multiple level extrusion coated, it is then dry simultaneously.
6. lithium ion battery according to claim 3, which is characterized in that the electrode active material coating extrusion coated
50% or more coated face density aim parameter is completed, then supplies remaining coated face density mesh with the technique suitable for thin-layer coating
Scalar.
7. lithium ion battery according to claim 6, which is characterized in that the technique suitable for thin-layer coating includes intaglio plate
One kind in printing, silk-screen printing, magnetron sputtering or ion plating.
8. lithium ion battery according to claim 7, which is characterized in that the magnetron sputtering technique uses electrode activity material
Material and conductive agent are respectively prepared two kinds of targets, two kinds of targets during magnetron sputtering cycle alternation as the target being sputtered,
By control the difference of two kinds of target holding time length ratios control deposit to electrode active material on electrode coating and
The component ratio of conductive agent.
9. a kind of consumer electronics product, including mobile phone and tablet computer, it is characterised in that containing described in claim 1 to 8
Lithium ion battery.
10. a kind of electric vehicle, it is characterised in that contain the lithium ion battery described in claim 1 to 8.
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Application publication date: 20180914 |