CN101615667B - Method and device for preparing battery pole piece - Google Patents
Method and device for preparing battery pole piece Download PDFInfo
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- CN101615667B CN101615667B CN2008101268356A CN200810126835A CN101615667B CN 101615667 B CN101615667 B CN 101615667B CN 2008101268356 A CN2008101268356 A CN 2008101268356A CN 200810126835 A CN200810126835 A CN 200810126835A CN 101615667 B CN101615667 B CN 101615667B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a method for preparing a battery pole piece. The method comprises the following steps: coating pole slurry on a current collecting body; and vibrating the obtained current collecting body coated with the pole slurry on the surface. The invention provides a device for preparing the battery pole piece. The device comprises a coating device and a vibrating device, wherein the pole slurry is coated on the surface of the current collecting body by the coating device, and the vibrating device is used for vibrating the current collecting body coated with the pole slurry on the surface. After being placed in a room with the temperature of 20+/-2 DEG C and the humidity of 20 percent-50 percent for 28 days in an open circuit, a battery with the volume of 4.2 V, which is prepared by the battery pole piece prepared by the device and the method, reduces the voltage by 5 mV at most, and the micro-short circuit rate tested by 20,000 batteries is 0.01 percent; and the battery prepared by a device and a method in the prior art has the voltage reduction up to 50 mV and the micro-short circuit rate of 0.05 percent under the completely same condition.
Description
Technical field
The device that the invention relates to a kind of preparation method of battery pole piece and realize this preparation method.
Background technology
During the conventional battery pole piece was produced, the device that adopts usually comprised applying device and the drying device that electrode slurry is coated in collection liquid surface.Therefore; Use method that this device prepares battery pole piece normally,, for example be attached with the coating wheel of electrode slurry at first through being attached with the applying device of electrode slurry; On collector, roll; Or the artificially is coated in electrode slurry on the collector, and wherein, said electrode slurry is a kind of slurries that contain active material and adhesive.After the coating, the collector that then surfaces coated that obtains is covered with electrode slurry carries out drying through drying device.Though this production method operation is simple, the battery pole piece that adopts this method to make usually causes using the self-discharge performance of the battery that this pole piece makes relatively poor, and has higher micro-short circuit rate.
Summary of the invention
The objective of the invention is for the shortcoming that the battery pole piece that overcomes prior art for preparing causes the self-discharge performance of battery relatively poor, the micro-short circuit rate is higher, provide a kind of self-discharge performance that makes battery better, the preparation method of battery pole piece that the micro-short circuit rate is lower and realize the device of this method.
The invention provides a kind of preparation method of battery pole piece, wherein, this method is included in coated electrode slurry on the collector, and the collector that the surfaces coated that obtains is covered with electrode slurry vibrates.
Device according to preparation battery pole piece of the present invention; This device comprises the applying device that is used for electrode slurry is coated to collection liquid surface; Wherein, this device is gone back the involving vibrations device, and the collector that said vibrating device is used for the surface is coated with electrode slurry vibrates.
Inventor of the present invention finds, among the preparation method of conventional battery pole piece, owing to what self existed in the preparation process; The reason of for example employed device itself as applying the installation site between wheel and the base wheel that is used for the tensioning collector, or applies the shape of wheel and basic wheel itself; Etc. the influence of factor, in addition, in electrode slurry, there is the uneven point of microcosmic; Though this uneven under the effect of electrode slurry self gravitation, also can carrying out freely replied; But required longer of time, often when also not returning back to formation state fully, the viscosity of electrode slurry self has changed or the electrode slurry that is applied on the collector is dried; In this case; This restoring force of slurry is weakened even is lost, thereby causes the coating layer thickness of the battery pole piece top electrode slurry that obtains inhomogeneous, and the thickness difference of the electrode slurry coating that applies on the electrode plates that causes making is generally up to 50% even higher; Can not satisfy the requirement of the requirement, particularly electrodes of lithium-ion batteries of the battery pole piece that the coating uniformity is had relatively high expectations.This mainly is to be covered with burr because of this on the battery pole piece because the thickness difference of the inhomogeneous generation of applied thickness shows as to make; Pierce through the battery diaphragm between battery anode slice and negative plate easily; Cause the seepage of sealing fluid; After long-time the placement, cause self-discharge of battery poor performance, micro-short circuit rate height, and then influence the quality of battery.
According to the preparation method and the device of battery pole piece provided by the invention, use applying device behind coated electrode slurry on the collector, with vibrating device the collector that the surfaces coated that obtains is covered with electrode slurry is vibrated; That is to say; Before this surfaces coated is covered with the collector drying of electrode slurry, increased the step of using vibrating device that the collector spreading mass is vibrated, therefore; According to the character that is coated in the electrode slurry on the collector; Like the density of electrode slurry, Gu factors such as tolerant content are selected suitable conditions such as vibration frequency, Oscillation Amplitude and time of vibration; This collector is vibrated, then can make microcosmic in the slurry uneven from freely replying under the effect of slurry self gravitation become under oscillating action, reply fast smooth.Then, the collector after using drying device to vibration carries out drying, carries out obtaining after the roll-in battery pole piece that the coated electrode slurry thickness difference in surface is no more than 15% even coating then.Owing to reduced burr, the battery that uses this battery pole piece to make has self-discharge performance and lower micro-short circuit rate preferably, has improved the performance of battery.For example; The capacity that is made by the battery pole piece that adopts apparatus and method provided by the invention to make is that 4.2 volts battery is opened a way in room temperature that to be shelved on humidity be under the 20-50% after 28 days for 20 ± 2 ℃ down; Cell voltage descends and is no more than 5 millivolts, and the micro-short circuit rate that records according to 20000 batteries is 0.01%; And under the identical situation of other conditionally complete, adopting the voltage of the battery that makes by one type of prior art syringe and method to descend up to 50 millivolts, the micro-short circuit rate is 0.05%.
Description of drawings
Fig. 1 is the sketch map according to the preparation method of battery pole piece provided by the invention;
Fig. 2 is the structural representation of the exemplary means used among the preparation method according to battery pole piece provided by the invention.
Embodiment
To combine accompanying drawing that the present invention is carried out detailed explanation below.
As depicted in figs. 1 and 2; The invention provides a kind of device that is used to prepare battery pole piece; This device comprises the applying device (not shown) that is used for electrode slurry is coated to collector 2 surfaces; It is characterized in that this device is gone back involving vibrations device 3, the collector 2 that said vibrating device 3 is used for the surface is coated with electrode slurry vibrates.
More particularly, the vibrational energy that said vibrating device 3 produces is evenly distributed on said collector 2 surfaces electrode slurrys that are positioned at said collector 2 surfaces, and then obtains thickness difference and be no more than 15% electrode slurry coating.
Wherein, said thickness difference is meant on the collector 2, and the difference of coating maximum ga(u)ge and coating minimum thickness is with respect to the percentage of coating maximum ga(u)ge, i.e. thickness difference=(coating maximum ga(u)ge value-coating minimum thickness value)/coating maximum ga(u)ge value * 100%.
As depicted in figs. 1 and 2, said collector 2 is divided into uncoated part 20 (collector before applying) and applies part 21 (collector after the coating) so that set forth.
Said applying device can be the various devices that can realize applying function, needs only required electrode slurry to be coated on collector 2 surfaces to obtain applying part 21.For example, said applying device can be to apply wheel.As a kind of execution mode, said applying device can comprise base wheel 1 and apply wheel, and wherein, said coating wheel is that the uncoated part 20 of said collector 2 applies to the collector 2 from base wheel 1.Said base wheel 1 is used for the said collector 2 of tensioning on the one hand, and the convenient wheel coated electrode slurry on collector 2 better that applies can also be used for transmitting continuously collector 2 on the other hand, can realize the continuous production of battery pole piece like this.In this case; Said coating wheel is preferably placed at the top of position between base wheel 1 and the vibrating device 3; Collector 2 after can guaranteeing like this to apply promptly applies part 21 and does not do and move up and down applying front-back direction, thereby can avoid moving because of this coating that causes that moves up and down.More preferably; Said coating wheel takes turns 1 directly over distance between the vibrating device 3 at said base; And should apply the side near base wheel 1 of the projection of wheel on collector 2 near vibrating device 3; Near vibrating device 3, again can because of the effect of vibrating device 3 not influence its coating simultaneously with sufficiently.Can make the coating part 21 of collector 2 after coated, obtain vibration as soon as possible like this; Reduce the slurry that applies on the part 21 and receive the time that action of gravity is freely replied; Improve operating efficiency, and more effectively impelled the uneven point of microcosmic in the slurry to reply smooth fast.
As shown in Figure 2; Said vibrating device 3 comprises at least one vibrating bin 30; This vibrating bin 30 comprises cover body 32 and vibration generating apparatus; The vibration that this vibration generating apparatus produces can make cover body 32 surfaces produce vibration, and is covered with the collector 2 of electrode slurry for the surfaces coated that contacts with cover body 32 surfaces this vibration transfer.
Wherein, This vibration generating apparatus can with said vibrating bin 30 inner or externally link to each other; During work, said vibration generating apparatus makes said vibrating bin 30 vibrate, and then passes through cover body 32 with on vibration transfer to the coating part 21 of said collector 2; The vibration frequency that makes said coating part 21 is 100-1000Hz, and amplitude is the 0.1-0.8 millimeter.
More particularly, said vibration generating apparatus can comprise motor 31 and eccentric wheel 34, and wherein, said eccentric wheel 34 links to each other with motor 31 electricity, and is fixed in the said cover body 32 through at least one support 33.After said motor 31 energisings; Driving is positioned at eccentric wheel 34 vibrations of the casing of vibrating bin 30; Drive vibrating bin 30 vibrations; And then the vibration that will produce is passed to said surfaces coated through cover body 32 and is covered with on the collector 2 of electrode slurry, make the particle that applies part 21 lip-deep slurries produce vibration, so the microcosmic in the slurry is uneven smooth from the quick answer under oscillating action under the effect of slurry self gravitation.
Under the preferable case, said vibrating device 3 can comprise a plurality of vibrating bins 30 that are arranged in order, and the distance between adjacent two vibrating bins 30 is 15-25 centimetre.Wherein, A face of the cover body 32 of said a plurality of vibrating bin 30 is on same horizontal plane; Promptly; Said a plurality of vibrating bin 30 and said surfaces coated are covered with the surface that the collector 2 of electrode slurry contacts and are positioned on the same horizontal plane; In the same plane all the time to keep said surfaces coated to be covered with the collector 2 of electrode slurry, avoided because surfaces coated is covered with electrode slurry that the deadweights of the collector 2 of coating itself cause heaps and then thickness skewness on collector 2 of the slurry that causes applying to the centre.More particularly; The cover body 32 of said vibration casing 30 and said surfaces coated are covered with surface that the collector 2 of electrode slurry contacts and the tangent plane of said base wheel 1 can be arranged to be positioned on the same horizontal plane; Overcome difference in height between said better to the adverse effect that causes of the electrode slurry of said collector 2 surface applied; For example because the difference in height between said, thereby make electrode slurry cause electrode slurry skewness on collector 2 moving the effect of gravity under.
In order to obtain to apply battery pole piece more uniformly, more preferably under the situation, in said a plurality of vibrating bins 30, have a vibrating bin 30 at least, the frequency of the vibration that this vibrating bin 30 produces is less than the frequency of the vibration that produces than these vibrating bin 30 more preceding vibrating bins 30.
A preferred embodiment of the invention; In said a plurality of vibrating bin 30; The frequency of the vibration that vibrating bin in back 30 produces also is that the vibration that said a plurality of vibrating bin 30 produces is the vibration that frequency is successively decreased successively less than the frequency of the vibration of previous vibrating bin 30 generations.
According to another kind of preferred implementation of the present invention, in said a plurality of vibrating bins 30, have a vibrating bin 30 at least, these vibrating bin 30 vibrative amplitudes are less than a vibrating bin 30 vibrative amplitudes more preceding than this vibrating bin 30.More preferably, in said a plurality of vibrating bins 30, the amplitude of the vibration that a back vibrating bin 30 produces also is that the vibration that said a plurality of vibrating bin 30 produces is the vibration that amplitude successively decreases less than the amplitude of the vibration of previous vibrating bin 30 generations.
As a kind of optimal way; In above-mentioned a plurality of vibrating bins 30; Has a vibrating bin 30 at least; The frequency of the vibration that this vibrating bin 30 produces and amplitude are all less than the frequency and the amplitude of the vibration of vibrating bins 30 generations more preceding than this vibrating bin 30; More preferably, the frequency of the vibration that the frequency of the vibration that a back vibrating bin 30 produces and amplitude all produce less than a back vibrating bin 30 and amplitude be all less than the vibration frequency and the amplitude of previous vibrating bin 30 generations, also is frequency and the vibration that amplitude all successively decreases of the vibration of said a plurality of vibrating bin 30 generations.
As a kind of preferred implementation; The frequency of the vibration that the vibrating bin 30 in the said vibrating device 3 produces can be 100-1000HZ; Amplitude can be the 0.1-0.8 millimeter; The number of said vibrating bin 30 can be 3-5, and the difference on the frequency of the vibration that produces of adjacent two vibrating bins 30 is 20-200Hz, and adjacent two vibrating bins, 30 vibrative difference of vibration are the 0.02-0.08 millimeter.
Under the preferable case, said cover body 32 with apply the smooth surface that part 21 contacts so that the collector 2 that said surfaces coated is covered with electrode slurry slips over from the surface of this cover body 32.For example, said cover body 32 can be the mirror face stainless steel cover body.
Especially, the area on the surface that said cover body 32 contacts with coating part 21 is not less than the area on the surface that is positioned at the coating part 21 on this cover body 32, can obtain the contact vibration in the maximum magnitude to guarantee said coating part 21, obtains more smooth product.
More particularly; When adopting 3 pairs of said collectors 2 of above-mentioned vibrating device to vibrate; As a kind of execution mode, it is to make collector 2 that said surfaces coated the is covered with electrode slurry surface through said cover body 32 continuously that said surfaces coated is covered with mode that the collector 2 of electrode slurry contacts with the surface of said cover body 32.Preferably, the radical length 22 of said coating part 21 is no more than the length of said cover body 32 in this direction.At this moment; Character according to the electrode slurry of said collector 2 surface applied; Like solid content; Factors such as weight are selected the suitable speed of the collector 2 of electrode slurry through said cover body 32 that this surfaces coated is covered with, and receive the vibration of enough time with each part on the coating part 21 that guarantees collector 2.Wherein, said radical length 22 refers to apply part 21 along the length on base wheel 1 axial direction.
As another kind of execution mode; When as batch production; Said surfaces coated is covered with mode that the collector 2 of electrode slurry contacts with the surface of said cover body 32 and places the surface of said cover body 32 for the collector 2 that said surfaces coated is covered with electrode slurry, and the entire area with said cover body 32 contact-making surfaces of the coating part 21 of wherein said collector 2 is no more than the entire area that self is had at the above cover body 32 of this contact-making surface.Can guarantee to apply part 21 each positions like this and all receive the vibration that comes from cover body 32.
According to another kind of execution mode, the vibration generating apparatus in the said vibrating device 3 externally is connected with said vibrating bin 30, promptly; This vibrating device 3 comprises motor 31, eccentric wheel 34 and vibration power shaft (not shown), and preferably, said motor 31 can be arranged to one with eccentric wheel 34; And link to each other with said vibrating bin 30 through the vibration power shaft, therefore, motor 31 energising drives eccentric wheels 34 and vibrates; Through vibrating power shaft with vibration transfer to vibrating bin 30; And then will vibrate through cover body 32 and be passed on the said coating part 21, more preferably, said vibration power shaft can link to each other with the cover body 32 of said vibrating bin 30; The vibration transfer that directly eccentric wheel 34 is produced and then drives coating part 21 vibrations that are positioned on the cover body 32 to this cover body 32.
Perhaps; Said vibrating device 3 can also be for comprising at least one flat board; The coating part 21 of collector 2 slips over from this planar surface, through vibration transfer to the said flat board of vibration power shaft with the vibration generating apparatus generation, and then drives said coating part 21 vibrations on this flat board.
Also such as, can also comprise amplifier on the power supply circuits of said vibrating device 3, can use less current to pass through the amplifier effect, the satisfactory vibration of generation, through the vibration power shaft with vibration transfer to applying on the part 21.
Preferably, device provided by the invention can also comprise the drying device (not shown), is used for the collector 2 that dry said surfaces coated is covered with electrode slurry.Under the preferable case, said drying device can be a baking oven, and dry temperature is generally 50-160 ℃, preferred 80-150 ℃.
Device below in conjunction with above-described preparation battery pole piece is further explained the method that this device used according to the invention prepares battery pole piece.
According to the method for preparing battery pole piece of the present invention, wherein, this method is included in coated electrode slurry on the collector 2, and the collector 2 that the surfaces coated that obtains is covered with electrode slurry vibrates.
More particularly, the method for said vibration instigates the electrode slurry that is positioned at said collector 2 surfaces to be evenly distributed on said collector 2 surfaces, obtains thickness difference and is no more than 15% electrode slurry coating.
According to the preparation method of battery pole piece provided by the invention, said battery pole piece can be an anode pole piece, also can be cathode pole piece.
When said battery pole piece was anode pole piece, said electrode slurry was the slurries that contain positive active material and adhesive, and said collector 2 can be the various conductive current collector that are suitable as lithium ion cell positive, for example can be aluminium foil.Said positive active material can be selected from the conventional positive active material of lithium secondary battery, like Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4In (wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur) one or more.The kind of said adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).In general, the content of positive active material is 40-80 weight % in the said slurries that contain positive active material and adhesive, is preferably 50-80 weight %; The content of said adhesive is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.The solvent that forms said slurries can be organic solvent or inorganic solvent, like among water, ethanol, DMF, the DMSO one or more.The amount of solvent can be positive active material and adhesive total weight 1-3 doubly, and make that solid content is 40-80 weight % in the solvent.
When said electrode plates was cathode pole piece, said electrode slurry was the slurries that contain negative electrode active material and adhesive, and said collector 2 can be for being suitable as the conductive current collector of lithium ion battery negative.The said conductive current collector that is suitable as lithium ion battery negative is conventionally known to one of skill in the art, for example can be selected from Copper Foil.Said negative electrode active material can be selected from the conventional negative electrode active material of lithium secondary battery, like in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more.Said adhesive can be selected from the conventional adhesive of lithium secondary battery, like in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR) one or more.In general, negative pole utmost point content of active substance is 40-80 weight % in the said slurries that contain negative electrode active material and adhesive, is preferably 50-80 weight %; The content of said adhesive is the 0.01-8 weight % of negative electrode active material, is preferably 1-5 weight %.Can also contain the negative pole auxiliary agent in the said slurries that contain negative electrode active material and adhesive; The kind of said negative pole auxiliary agent and content are conventionally known to one of skill in the art; For example, said negative pole auxiliary agent can be selected from conductive agent, like in acetylene black, conductive carbon black, the electrically conductive graphite one or more; Its content is the 0-15 weight % of negative electrode active material, is preferably 0-10 weight %.The solvent that forms said slurries can be organic solvent or inorganic solvent, like among water, ethanol, DMF, the DMSO one or more.The amount of said solvent makes that solid content is 40-80 weight % in the solvent.Said solid content is meant that the quality that adds solid matter in the electrode slurry accounts for the ratio of all material masses.
Comprise according to the preparation method of battery pole piece of the present invention electrode slurry is applied on the surface of collector 2.Said coating method can be that spraying, roller coat or other are applied to the method on the said collector 2 with electrode slurry.For the labor savings of enhancing productivity, preferred said coating applies through using applying device.As a kind of execution mode, can roll on collector 2 surfaces with the coating wheel (not shown) that is attached with electrode slurry, said electrode slurry is applied on the uncoated part 20 of said collector 2.
Saidly surfaces coated is covered with method that the collector 2 of electrode slurry vibrates is meant the coating part 21 of collector 2 is vibrated; Be dried at the said slurry that is coated on the said collector 2 and by roll-in after, the thickness difference of the electrode plates top electrode slurry coating of acquisition is no more than 15%.Wherein, the condition of said vibration, like vibration frequency, amplitude and time of vibration etc., for according to being coated in the character of the electrode slurry on the said collector 2, the density of this electrode slurry for example, difference such as solid content and selecting.Usually, the solid content of said electrode slurry is 40-80 weight %, and viscosity is 4000-8000cp, and it is the 0.12-0.17 millimeter that the coating amount of said electrode slurry makes the thickness of the battery pole piece that makes.
According to the present invention; At vibration condition is that vibration frequency is 100-1000Hz; Amplitude is the 0.1-0.8 millimeter, under time of vibration 0.5-5 minute the situation, just can make the particle of the electrode slurry on the coating part 21 of said collector 2 reply smooth fast; Slurry is evenly distributed on this coating part 21, and then the thickness difference of the coating that obtains is no more than 15% uniform battery pole piece.Simultaneously, inventor of the present invention finds that also in above-mentioned scope, vibration frequency is big more, and amplitude is more little, and is favourable more to battery pole piece.Preferably, the frequency of said vibration is 300-800Hz, when amplitude is the 0.2-0.5 millimeter, only need be 1.5-2.5 minute vibration the time of carrying out, and can further reduce the thickness difference of coating, improves the uniformity of electrode material coating.Wherein, the frequency of said vibration is meant the vibration frequency of the coating part 21 of said collector 2, and said amplitude is the amplitude of the coating part 21 of said collector 2.Because less as the thickness of the thickness of the collector 2 of battery pole piece and cover body 32 among the present invention, therefore lighter weight it is generally acknowledged the vibration frequency and the amplitude of the coating part 21 that vibration frequencies that vibrating device 3 is provided with itself and amplitude are collector 2.Therefore, can directly control said vibrating device 3 makes the vibration frequency that applies part 21 and amplitude in scope of the present invention.Big when collector 2 and cover body 32 thickness, when weight is big, can suitably increase the frequency and the amplitude of vibration according to specific circumstances, the frequency and the amplitude that make the vibration that collector 2 receives are in scope of the present invention.
Wherein, In order to obtain to apply more evenly battery pole piece, it can be that the surface is coated with the collector 2 of electrode slurry or the various piece that the surface is coated with the collector 2 of electrode slurry is repeatedly vibrated respectively that the surface is coated with method that the collector 2 of electrode slurry vibrates.More particularly, in the said repeatedly vibration, the time interval between adjacent twice vibration can be 0.075-0.25 minute.Preferably; In the said repeatedly vibration, have once vibration at least, the frequency of this vibration is less than the once frequency of vibration more preceding than this vibration; More preferably; In the said repeatedly vibration, after once the frequency of vibration also be the said repeatedly vibration vibration of successively decreasing successively less than the preceding once frequency of vibration for frequency.
Perhaps, the amplitude of this vibration is less than than the more preceding once amplitude of vibration of this vibration, more preferably, in the said repeatedly vibration, after once the amplitude of vibration also be that said vibration is the vibration that amplitude successively decreases less than the preceding once amplitude of vibration.As preferred embodiment, in said repeatedly vibration, after once frequency and the amplitude of vibration is all less than the preceding once frequency and the amplitude of vibration, more preferably, said vibration frequency and the amplitude that repeatedly vibrates all successively decreases successively.
Specifically, in the preparation in accordance with the present invention, receive the repeatedly vibration that vibration frequency and amplitude all successively decrease successively on the coating part 21.Preferably, carry out 3-5 vibration to applying part 21, wherein, the vibration frequency difference of adjacent twice vibration is 20-200Hz, and the difference of vibration of adjacent twice vibration is the 0.02-0.08 millimeter.
In addition; Before the electrode slurry that on said collector 2, applies is dried; At least the coating part of this collector 2 21 is supported by said vibrating device 3, makes the electrode slurry of coating on the said collector 2 can not receive the influence of action of gravity and to the centre heap, can before being dried, keep smooth.Therefore, use preparation in accordance with the present invention can obtain the uniform battery pole piece of thickness, the self-discharge performance of the battery that obtains through this pole piece better and the micro-short circuit rate lower, have higher performance.
For accelerating electrode slurry fixing on collector 2, can also comprise drying means according to the preparation method of battery pole piece of the present invention.Said drying means can use baking oven to carry out drying, and dry temperature is generally 50-160 ℃, preferred 80-150 ℃
Can find out from above description; Use the device of preparation battery pole piece provided by the invention to prepare the method for battery pole piece; Apply on collector 2 with applying device as electrode plates; The collector 2 that surfaces coated through 3 pairs of acquisitions of vibrating device is covered with electrode slurry vibrates, and then carries out drying.On the one hand; Compare with freely replying of under the self gravitation effect, carrying out, it is smooth that the oscillating action that this external force drives can make the microcosmic particle in the electrode slurry that is coated on the collector 2 reply in the short period of time, simultaneously; Reason own in the process that battery pole piece is made can offset or reduce to this vibration; For example, electrode slurry is applied in the applying device on the collector 2, applies wheel and take turns the installation site between 1 with the base that is used for tensioning collector 2; Or apply the influence of the shape etc. of wheel and base wheel 1 itself, cause the electrode slurry that is coated on the collector 2 inhomogeneous.Subsequently; After the collector that is coated with electrode slurry 2 of above acquisition carried out drying and roll-in; Said electrode slurry is no more than 15% distributions with thickness difference on collector 2 even, thereby obtain the uniform battery pole piece of surperficial slurry coating, reduced burr; And then it is lower to obtain self-discharge performance, the battery that the micro-short circuit rate is lower.
The apparatus and method of the battery pole piece of preparation are provided according to the present invention, especially, can be applied in the preparation process of electrodes of lithium-ion batteries.
Below, will with the lithium ion battery example, explained in detail is used the apparatus and method of the uniform electrodes of lithium-ion batteries of preparation thickness provided by the invention.
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
The device that is used to prepare battery pole piece is as depicted in figs. 1 and 2.Vibrating device 3 comprises that 5 are arranged in order identical vibrating bin 30 (BYD produces: model is the vibrating device of LB-2008A), and wherein, the distance between the adjacent vibrating bin 30 is 15 centimetres.Said vibrating bin 30 comprises cover body 32, and this cover body 32 is a stainless steel material, is of a size of centimetre (wide) * 17,100 centimetres of (length) * 50 centimetre (height).
Applying device comprises base wheel 1 and applies the wheel (not shown).The radius of said base wheel 1 is the 100-200 millimeter, and vertically wide is the 400-600 millimeter.Axial edge and the vibrating device 3 the shortest outer peripheral horizontal ranges of this base wheel 1 are 30 centimetres, and the center line of vibrating bin 30 on wide be through said base wheel 1 mid point in the axial direction, and the cover body 32 of vibrating bin 30 and base are taken turns 1 tangent plane on same horizontal plane.Said coating wheel radius is 60 millimeters, and wide vertically and base wheel 1 be with wide, and this coatings wheel is arranged at collector 2 and leaves base wheel 1 and be sent to directly over nearest vibrating device 3 part before.The minimum point place tangent plane of coating wheel is 0.16 millimeter to the distance on plane, collector 2 place.
Baking oven is that the model that BYD produces is the baking oven of BYD-LJ001.Rolling device is that to receive the model of section's Nore production be the LDHY800-PH75 roll squeezer.
Electrode slurry is a lithium ion battery anode glue size, battery anode slurry consist of positive active material LiCoO
2, adhesive polyvinylidene fluoride (PVDF) and water, the said positive active material LiCoO that contains
2In the slurries of adhesive polyvinylidene fluoride (PVDF), positive active material LiCoO
2Content be 60 weight %, said adhesive polyvinylidene fluoride (PVDF) content is positive active material utmost point active material LiCoO
22 weight %, surplus is an aqueous solvent.Solid content is 70%, and viscosity is 5000cp.
To apply wheel be 1000 mm/min with linear velocity is applied to above-mentioned electrode slurry on the surface as the aluminium foil of collector 2.The transfer rate of said collector 2 is 1000 mm/min; Applying part 21 is that the speed of 1000 mm/min is through said vibrating device 3 with speed also; That is, to total time of the vibration that applies part 21 be 5 minutes, the time interval between adjacent twice vibration is 0.15 minute.And the frequency of the vibration that coating part 21 receives is followed successively by 1000Hz, 980Hz, 960Hz, 940Hz and 920Hz, and amplitude is followed successively by 0.18 millimeter, 0.16 millimeter, 0.14 millimeter, 0.12 millimeter and 0.1 millimeter.
The collector 2 that is covered with electrode slurry through the surfaces coated of vibration was dried 2 minutes in temperature is 100 ℃ baking oven, measured its thickness with using Britain to be prone to high 124 surface thickness measuring instruments (range 0-1000 micron) after dried collector 2 roll-ins then.Cut respectively and grow into 500 millimeters, wide is 40 millimeters positive plate, the LiCoO of this positive plate
2Content be 7.8 the gram.
Comparative Examples 1
Prepare battery pole piece according to embodiment 1 said apparatus and method, different is, not to the collector 2 after applying, does not promptly vibrate applying part 21, just sends into baking oven and carries out drying, obtains positive active material LiCoO
2Content be 7.8 the gram positive plate.
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
Prepare battery pole piece according to embodiment 1 said apparatus and method, different is,
The number of said vibrating bin 30 is 3.
To apply wheel be 2000 mm/min with linear velocity is applied to above-mentioned electrode slurry on the surface as the aluminium foil of collector 2.The transfer rate of said collector 2 is 2000 mm/min; Applying part 21 is that the speed of 2000 mm/min is through said vibrating device 3 with speed also; That is, to total time of the vibration that applies part 21 be 1.5 minutes, the time interval between adjacent twice vibration is 0.075 minute.And the frequency of the vibration that coating part 21 receives is followed successively by 800Hz, 700Hz, 600Hz, and amplitude is followed successively by 0.3 millimeter, 0.25 millimeter and 0.20 millimeter.
Embodiment 3
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
Prepare battery pole piece according to embodiment 1 said apparatus and method, different is,
The number of said vibrating bin 30 is 1.
Applying wheel is applied to above-mentioned electrode slurry as after on the surface of the aluminium foil of collector 2; On the collector that obtains 2, be at least and apply part 21 and place on the surface of vibrating device 3 and vibrate, wherein vibration frequency is 900Hz; Amplitude is 0.7 millimeter, and time of vibration is 0.5 minute.
Embodiment 4
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
Prepare battery pole piece according to embodiment 1 said apparatus and method, different is,
The number of said vibrating bin 30 is 4, and the distance between these two vibrating bins 30 is 25 centimetres.
Said electrode slurry is a lithium ion battery cathode slurry; Lithium ion battery cathode slurry consist of negative electrode active material Delanium, adhesive polyvinylidene fluoride (PVDF), negative pole auxiliary agent conductive carbon black, He Shui, the content of negative electrode active material is 60 weight % in the said cathode size; The content of said adhesive is 2 weight % of negative electrode active material Delanium; The content of said negative pole auxiliary agent conductive carbon black is 8 weight % of negative electrode active material Delanium, and surplus is a water.Solid content is 70%, and viscosity is 5000cp.
Applying wheel is applied to above-mentioned electrode slurry on the surface as the Copper Foil of collector 2 with the speed of linear velocity 1600 mm/min.The transfer rate of collector 2 is 1600 mm/min; Applying part 21 is that the speed of 1600 mm/min is through said vibrating device 3 with speed also; That is, to total time of the vibration that applies part 21 be 2.5 minutes, the time interval between adjacent twice vibration is about 0.16 minute.And the frequency of the vibration that coating part 21 receives is followed successively by 700Hz, 500Hz, 300Hz and 100Hz, and amplitude respectively is 0.8 millimeter, 0.72 millimeter, 0.64 millimeter, 0.56 millimeter.
The collector 2 that is covered with electrode slurry through the surfaces coated of vibration was the baking oven inner drying of 100 ℃ of temperature 2 minutes; Then with dried collector 2 roll-ins, cut and grow into 500 millimeters; Wide is 40 millimeters battery cathode sheet, and the content of negative electrode active material Delanium is 3.9 grams on each negative plate.
Comparative Examples 2
Prepare the device of battery pole piece and adopt this device to prepare the method for battery pole piece according to embodiment 4 described uses; Different is; Not to the collector 2 after applying; Promptly do not vibrate applying part 21, just send into baking oven and carry out drying, the content that obtains the negative electrode active material Delanium is the negative plate of 3.9 grams.
Embodiment 5
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
Prepare battery pole piece according to embodiment 4 said apparatus and method, different is,
The number of said vibrating bin 30 is 2.
Applying wheel is applied to above-mentioned electrode slurry on the surface as the Copper Foil of collector 2 with the speed of linear velocity 1000 mm/min.The transfer rate of collector 2 is 1000 mm/min; The collector 2 that surfaces coated is covered with electrode slurry is that the speed of 1000 mm/min is through said vibrating device 3 with speed also; Promptly; For being about 2 minutes, the time interval between adjacent twice vibration is 0.25 minute to the time of vibration that applies part 21.And the frequency of the vibration that coating part 21 receives is followed successively by 450Hz, and 300Hz, amplitude are followed successively by 0.5 millimeter, 0.44 millimeter.
Embodiment 6
Embodiment 6
This embodiment is used to explain the apparatus and method that are used to prepare battery pole piece provided by the invention.
Prepare battery pole piece according to embodiment 4 said apparatus and method, different is,
Applying wheel is applied to above-mentioned electrode slurry as after on the surface of the Copper Foil of collector 2; On the collector that obtains 2, be at least and apply part 21 and place on the surface of vibrating device 3 and vibrate, wherein vibration frequency is 200Hz; Amplitude is 0.4 millimeter, and time of vibration is 1 minute.
Performance test
Slurry uniformity: use Britain to be prone to high 124 surface thickness measuring instruments (range 0-1000 micron) measurement thickness respectively with the battery pole piece that Comparative Examples 1 makes embodiment 1, obtain coating maximum ga(u)ge and minimum thickness.The result lists in the table 1.
Table 1
| Project | Pole piece | The coating maximum ga(u)ge | The coating minimum thickness | |
| Embodiment | ||||
| 1 | Positive plate | 0.145 millimeter | 0.140 millimeter | 3.4％ |
| Comparative Examples 1 | Positive plate | 0.146 millimeter | 0.067 millimeter | 54.1 |
| Embodiment | ||||
| 2 | Positive plate | 0.148 millimeter | 0.136 millimeter | 8.1％ |
| Embodiment 3 | Positive plate | 0.155 millimeter | 0.137 millimeter | 11.6％ |
| Embodiment 4 | Negative plate | 0.150 millimeter | 0.137 millimeter | 8.7％ |
| Comparative Examples 2 | Negative plate | 0.167 millimeter | 0.088 millimeter | 47.3％ |
| Embodiment 5 | Negative plate | 0.152 millimeter | 0.136 millimeter | 10.5％ |
| Embodiment 6 | Negative plate | 0.160 millimeter | 0.140 millimeter | 12.5％ |
Self-discharge of battery property:
Use above-mentioned positive plate, negative plate and polypropylene screen to be wound into the pole piece of square lithium ion battery according to the mode of following table 2 respectively, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with the amount of 3.8g/Ah, seal, process the square lithium ion battery of LP053450ARUL.Use above-mentioned positive and negative plate respectively to prepare 20000 identical batteries by the mode of table 1.
With the lithium ion battery that obtains 100% charging back (battery capacity is 4.2 volts), together being shelved on temperature by open circuit is 20 ± 2 ℃, and humidity is following 28 days of 20-50% condition, measures cell voltage through BYD capacity check cabinet again.Wherein, cell voltage reduction rate=(the 4.2-∑ is respectively organized magnitude of voltage/20000)/4.2 * 100%.
Table 2
| The battery numbering | The positive plate source | The negative plate source | Cell voltage reduction amount | Cell voltage reduction |
| S1 | Embodiment | |||
| 1 | Embodiment 4 | 5 millivolts | 0.15％ | |
| CS1 | Comparative Examples 1 | Embodiment 4 | 20 millivolts | 0.48％ |
| CS2 | Comparative Examples 1 | Comparative Examples 2 | 50 millivolts | 1.19 |
| CS3 | Embodiment | |||
| 1 | Comparative Examples 2 | 18 millivolts | 0.43 | |
| S2 | Embodiment | |||
| 2 | Embodiment 5 | 8 millivolts | 0.19％ | |
| S3 | Embodiment 3 | Embodiment 6 | 12 millivolts | 0.29％ |
The micro-short circuit rate of battery:
Use above-mentioned positive plate, negative plate and polypropylene screen to be wound into the pole piece of square lithium ion battery according to the mode of table 3 respectively, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with the amount of 3.8g/Ah, seal, process the square lithium ion battery of LP053450ARUL.Use above-mentioned positive and negative plate respectively to prepare 20000 identical batteries by the mode of table 2.
Assay method is: survey with universal instrument earlier, internal resistance is all greater than 20 megaohms, and the direct current with 150V impacts again, adopts universal instrument to survey the internal resistance of cell after the impact again, and internal resistance is the micro-short circuit battery less than the battery of 20 megaohms.Sort out the battery that micro-short circuit takes place in 20000 batteries, then, the battery that micro-short circuit takes place is taken apart, analyze the reason that micro-short circuit takes place for it, obtain because pole piece surface burr diaphragm causes the number of the battery of internal short-circuit of battery.The result lists in the table 2, and wherein, the micro-short circuit rate refers to because pole piece burr diaphragm causes the short circuit ratio of internal short-circuit of battery, i.e. micro-short circuit rate=because battery number/20000 * 100% that pole piece burr diaphragm causes the inside battery micro-short circuit.
Table 3
| The battery numbering | The positive plate source | The negative plate source | The micro-short circuit |
| S1 | Embodiment | ||
| 1 | Embodiment 4 | 0.01％ | |
| CS1 | Comparative Examples 1 | Embodiment 4 | 0.04％ |
| CS2 | Comparative Examples 1 | Comparative Examples 2 | 0.05 |
| CS3 | Embodiment | ||
| 1 | Comparative Examples 2 | 0.04 | |
| S2 | Embodiment | ||
| 2 | Embodiment 5 | 0.02％ | |
| S3 | Embodiment 3 | Embodiment 6 | 0.02％ |
Can find out from the result of table 1-table 3; Adopt method provided by the invention can make the coating layer thickness difference and be no more than 15% and the uniform battery pole piece of distributions of electrode slurry; Thereby reduced to be distributed in the burr on the collector, obtained the battery that the self discharge amount is less, the micro-short circuit rate is lower.And prior art causes the self discharge amount of battery bigger, and has higher micro-short circuit rate because therefore involving vibrations step not can not obtain the battery pole piece that electrode slurry is evenly distributed.
Claims (20)
1. the preparation method of a battery pole piece; It is characterized in that; This method is included in coated electrode slurry on the collector, and the collector that the surfaces coated that obtains is covered with electrode slurry vibrates, wherein; Said vibration is evenly distributed on the said collection liquid surface electrode slurry that is positioned at said collection liquid surface, obtains thickness difference and is no more than 15% electrode slurry coating; The frequency of said vibration is 300-800Hz, and amplitude is the 0.2-0.5 millimeter, and time of vibration is 1.5-2.5 minute.
2. according to any described preparation method in the claim 1; Wherein, surfaces coated being covered with method that the collector of electrode slurry vibrates comprises the surface is coated with the collector of electrode slurry or the various piece that the surface is coated with the collector of electrode slurry is repeatedly vibrated respectively.
3. preparation method according to claim 2, wherein, in the said repeatedly vibration, the time interval between adjacent twice vibration is 0.075-0.25 minute.
4. preparation method according to claim 3 wherein, in the said repeatedly vibration, has once vibration at least, and the frequency of this vibration is less than the once frequency of vibration more preceding than this vibration.
5. preparation method according to claim 4, wherein, said repeatedly the vibration in, after once the vibration frequency less than preceding once the vibration frequency.
6. preparation method according to claim 3 wherein, in the said repeatedly vibration, has once vibration at least, and the amplitude of this vibration is less than the once amplitude of vibration more preceding than this vibration.
7. preparation method according to claim 6, wherein, said repeatedly the vibration in, after once the vibration amplitude less than preceding once the vibration amplitude.
8. according to any described preparation method among the claim 3-7, wherein, vibration number is 3-5 time, and the difference on the frequency of adjacent twice vibration is 20-200Hz, and the difference of vibration of adjacent twice vibration is the 0.02-0.08 millimeter.
9. preparation method according to claim 8, wherein, the solid content of said electrode slurry is 40-80 weight %, and viscosity is 4000-8000cp, and it is the 0.12-0.17 millimeter that the coating amount of said electrode slurry makes the thickness of the battery pole piece that makes.
10. the preparation facilities of a battery pole piece; This device comprises the applying device that is used for electrode slurry is coated to collection liquid surface, it is characterized in that, this device is gone back the involving vibrations device; The collector that said vibrating device is used for the surface is coated with electrode slurry vibrates; The frequency of said vibration is 300-800Hz, and amplitude is the 0.2-0.5 millimeter, and time of vibration is 1.5-2.5 minute.
11. device according to claim 10; Wherein, Said vibrating device comprises at least one vibrating bin; This vibrating bin comprises cover body and vibration generating apparatus, and the vibration that this vibration generating apparatus produces makes the cover body surface produce vibration, and is covered with the collector of electrode slurry for the surfaces coated that contacts with the cover body surface this vibration transfer.
12. device according to claim 11, wherein, said vibration generating apparatus comprises motor and eccentric wheel, and said motor is electrically connected with eccentric wheel, and said eccentric wheel is fixed in the said cover body through at least one support.
13. device according to claim 11, wherein, said vibrating bin is a plurality of, and these a plurality of vibrating bins are arranged in order, and the distance between adjacent two vibrating bins is 15-25 centimetre.
14. device according to claim 13 wherein, in said a plurality of vibrating bins, has a vibrating bin at least, the frequency of the vibration that this vibrating bin produces is less than the frequency of the vibration of a vibrating bin generation more preceding than this vibrating bin.
15. device according to claim 14, wherein, in said a plurality of vibrating bins, the frequency of the vibration that a back vibrating bin produces is less than the frequency of the vibration of previous vibrating bin generation.
16. device according to claim 13 wherein, in said a plurality of vibrating bins, has a vibrating bin at least, the amplitude of the vibration that this vibrating bin produces is less than the amplitude of the vibration of a vibrating bin generation more preceding than this vibrating bin.
17. device according to claim 16, wherein, in said a plurality of vibrating bins, the amplitude of the vibration that a back vibrating bin produces is less than the amplitude of the vibration of previous vibrating bin generation.
18. according to any described device among the claim 13-17; Wherein, The frequency of the vibration that said vibrating bin produces is 100-1000HZ, and amplitude is the 0.1-0.8 millimeter, and the number of said vibrating bin is 3-5; And the difference on the frequency of the vibration that adjacent two vibrating bins produce is 20-200Hz, and adjacent two vibrative difference of vibration of vibrating bin are the 0.02-0.08 millimeter.
19. device according to claim 13, wherein, a face of the cover body of said a plurality of vibrating bins is on same horizontal plane.
20. device according to claim 10, wherein, said applying device comprises base wheel and coating wheel, and said base wheel is used for tensioning collector and the continuous collector that transmits, and said coating wheel applies the collector from the base wheel.
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| CN112103462B (en) * | 2020-09-03 | 2021-06-29 | 江西省中子能源有限公司 | Improved operation method for electrode slurry drawing of lithium ion battery |
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