CN110346727A - The method and lithium ion battery of monitoring, analysis anode slice of lithium ion battery rebound - Google Patents
The method and lithium ion battery of monitoring, analysis anode slice of lithium ion battery rebound Download PDFInfo
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- CN110346727A CN110346727A CN201910507471.4A CN201910507471A CN110346727A CN 110346727 A CN110346727 A CN 110346727A CN 201910507471 A CN201910507471 A CN 201910507471A CN 110346727 A CN110346727 A CN 110346727A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B21/00—Measuring arrangements or details thereof, where the measuring technique is not covered by the other groups of this subclass, unspecified or not relevant
- G01B21/02—Measuring arrangements or details thereof, where the measuring technique is not covered by the other groups of this subclass, unspecified or not relevant for measuring length, width, or thickness
- G01B21/08—Measuring arrangements or details thereof, where the measuring technique is not covered by the other groups of this subclass, unspecified or not relevant for measuring length, width, or thickness for measuring thickness
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
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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
This application involves the methods and lithium ion battery of monitoring, analysis anode slice of lithium ion battery rebound.The lithium ion battery includes anode pole piece comprising the positive electrode coating arranged on the two sides of positive foil；Cathode pole piece comprising the negative electrode material coating arranged on the two sides of cathode foil；And diaphragm, wherein, the diaphragm is between anode pole piece and cathode pole piece, wherein, the lithium ion battery further comprises the barrier of intermittent arrangement, to be formed with the first area with the barrier and the second area without the barrier, wherein, the barrier along anode pole piece long axis direction compartment of terrain in the side perpendicular to the long axis upward around coating the anode pole piece, or be discontinuously arranged between anode pole piece and diaphragm or be discontinuously arranged between cathode pole piece and diaphragm.The application further relates to optimize positive electrode according to method and lithium ion battery that anode slice of lithium ion battery rebounds.
Description
Technical field
This application involves the characterizations of lithium ion battery material test, more particularly, to a kind of monitoring, analysis lithium ion battery
The method and lithium ion battery of anode pole piece rebound.
Background technique
Anode material for lithium ion battery mainly has metal oxide, polyanionic salt, fluoride and sulfide etc., currently
Commercialization mainly has LiCoO2、LiMn2O4、LiFePO4、LiNixCoyMn1-x-yO2And LiNixCoyAl1-x-yO2Equal positive electrodes,
By crystal structure point, positive electrode has layer structure, spinel structure and olivine structural etc.；When roll-in, equipment and pole piece are sent out
Raw energy transmission occurs energy loss, while storing elastic potential energy, rebound phase of the elastic potential energy after roll-in by roll-in pole piece
Gradually it is released；Meanwhile a series of variations can occur in battery charge and discharge process for pole piece, for example, positive electrode elemental constituent
Change, dissolving metal, the change of element valence, the variation of crystal structure, the change of Cohesive Energy, primary particle generate
Crackle, second particle structure change and destroy, and particulate interspaces increase, and particle surface, pattern change, PVDF degradation, swelling,
The side reaction with electrolyte of positive plate related component, pole piece structure destroy.It is apparent that these factors can cause pole piece to have
Rebound.If the rebound of pole piece is larger, closing and the battery performance of battery core may be will affect, or even cause safety problem.
Therefore the rebound to the anode of battery is needed to be controlled.The design of battery, the rebound of battery being made to pole piece
With vital influence.
Currently, the variation for mainly monitoring rebound rate by test anode pole piece thickness in the industry obtains the change of pole piece thickness
Change trend, but anode pole piece thickness change is lacked and is deeply clearly recognized, obtained result is to the improvement optimization of material, battery
Design and the use of material lack strong support, and in this case, the battery product period for researching and developing optimization is long, at high cost.
Summary of the invention
In view of this, it is a primary object of the present invention at least one of solve the above problems.For this purpose, the present invention provides
A kind of analysis method of anode slice of lithium ion battery rebound and lithium ion battery for this method.Side through the invention
Method and lithium ion battery can distinguish the physics rebound and chemistry rebound of anode pole piece, and distinguish test monitoring, to be
Process is made in battery design, optimization materials'use scheme and battery and control process provides parameter.
In order to achieve the above objectives, the present invention provides following technical solutions.
The first aspect of the present invention is the provision of a kind of lithium ion for the rebound monitoring of lithium ion cell positive thickness
Battery, comprising:
Anode pole piece, the anode pole piece include the negative electrode material coating continuously arranged on the two sides of positive foil；
Cathode pole piece, the cathode pole piece include the negative electrode material coating continuously arranged on the two sides of cathode foil；With
Diaphragm,
Wherein, two sides of the anode pole piece with positive electrode coating and cathode pole piece have the two of negative electrode material coating
Side is positioned opposite, and the diaphragm is arranged between the anode pole piece and the cathode pole piece,
Wherein, the lithium ion battery further comprises barrier, the barrier intermittent arrangement so that the lithium from
Sub- battery is formed with the first area with the barrier and the second area without the barrier,
Wherein, the barrier is along anode pole piece long axis direction compartment of terrain perpendicular to the square upward around packet of the long axis
It covers the anode pole piece or the barrier is discontinuously arranged between the anode pole piece and the diaphragm or discontinuously sets
It sets between the cathode pole piece and the diaphragm.
According to one embodiment, the barrier is insulating tape or insulating film.
According to one embodiment, the barrier with a thickness of 1~10 micron, preferably 4~6 microns.
According to one embodiment, the length ratio of the first area and second area is 1:3~3:1, and described the
One region and the second area are alternately distributed.
According to one embodiment, the lithium ion battery is coiled battery, or is laminated battery plate.
According to one embodiment, the coiled battery bending place is the second area of the no barrier.
The second aspect of the present invention is the provision of the method that a kind of pair of lithium ion cell positive thickness rebound is monitored,
Wherein, it the described method comprises the following steps:
The lithium ion battery described in the first aspect of the present invention measures positive foil in the lithium ion battery respectively
Thickness DN- foil, anode pole piece thickness D after roll-inN- 0, after battery charging for the first time when discharging, the thickness of first area anode pole piece
D1-1, the thickness D of second area anode pole piece2-1, at circulating battery n weeks, first area anode thickness D1-n, second area anode
Thickness D2-n；The n value is 2~2500, and
Rebound rate is calculated, according to measured DN- foil、DN- 0、D1-1、D2-1、D1-n、D2-nAnode is calculated separately as follows
Pole piece physics rebound rate αN- object, anode pole piece entirety rebound rate αIt is n- wholeAnd anode pole piece chemistry rebound rate αN-ization, wherein it is described
Anode pole piece chemistry rebound rate αN-izationIt is obtained by formula III:
αN- object=(D1-n-DN- 0)/(DN- 0-DN- foil) (I)
αIt is n- whole=(D2-n-DN- 0)/(DN- 0-DN- foil) (II)
αN-ization=(D2-n-D1-1)/(D1-1-DN- foil) (III)。
Wherein, the n value is preferably 20~800.
According to a kind of embodiment, the anode pole piece physics rebound rate α to obtainN- object, anode pole piece entirety rebound rate αIt is n- whole
And anode pole piece chemistry rebound rate αN-izationIt maps respectively to minute, obtains the corresponding rebound rate of anode pole piece with charge and discharge
Circulation change curve graph.
Another aspect of the present invention is the provision of the method that a kind of pair of anode slice of lithium ion battery optimizes, including
Following steps:
The rebound of lithium ion cell positive thickness is monitored with method according to a second aspect of the present invention,
According to anode pole piece physics rebound rate αN- object, anode pole piece chemistry rebound rate αN-izationAnd/or anode pole piece integrally rebounds
Rate αIt is n- wholeWith the Variation Features of charge and discharge cycles number, the physics, chemistry and whole rebound of anode pole piece are monitored.
According to one embodiment, the object that the method passes through the monitoring anode pole piece according to a second aspect of the present invention
Reason, chemistry and integrally rebound as a result, to the optimization of material for lithium ion battery, material type selecting, battery design, materials'use
Technique improves.
The present invention monitors the lithium ion battery of positive thickness rebound by providing, and can distinguish the object of anode
Reason rebound and chemistry rebound, so as to clear positive electrode in cyclic process, the differentiation of physics rebound and chemistry rebound becomes
Gesture, and to the contribution rate integrally to rebound, so as to targetedly be adjusted and optimize to positive electrode.It is opened in battery
In the hair stage, can rebound to different materials size look-ahead, rapid evaluation different materials ballistic properties superiority and inferiority, guiding material type selecting
To accelerate the R&D cycle of battery product, research and development cost has been saved.
Detailed description of the invention
Fig. 1 is according to barrier layer schematic top plan view in anode pole piece of the present invention rebound monitoring；
Fig. 2A is the side according to the lithium ion battery (wherein, barrier layer clad anode pole piece) of one embodiment of the present invention
Depending on schematic diagram；Fig. 2 B is (wherein, to be obstructed according to the lithium ion battery of an embodiment in anode pole piece of the present invention rebound monitoring
Layer clad anode pole piece) the direction A-A diagrammatic cross-section；Fig. 2 C is according to positive and negative in anode pole piece of the present invention rebound monitoring
Pole pole piece coiling at core schematic diagram；
Fig. 3 A is that (wherein, barrier layer is located at diaphragm to another embodiment according in anode pole piece of the present invention rebound monitoring
By anode pole piece side) lithium ion battery schematic side view；Fig. 3 B is according to another in anode pole piece of the present invention rebound monitoring
The diagrammatic cross-section in the direction A-A of the lithium ion battery (wherein, barrier layer is located at diaphragm by anode pole piece side) of a embodiment；
Fig. 4 A is that (wherein, barrier layer is located at diaphragm to another embodiment according in anode pole piece of the present invention rebound monitoring
By cathode pole piece side) lithium ion battery schematic side view；Fig. 4 B is according to another in anode pole piece of the present invention rebound monitoring
The diagrammatic cross-section in the direction A-A of the lithium ion battery (wherein, barrier layer is located at diaphragm by cathode pole piece side) of a embodiment；
Fig. 5 show A material compacted density be 3.45g/cm3When corresponding physics rebound, chemistry rebound and whole
The curve graph to rebound with test point.
Fig. 6 show A material compacted density be 2.85g/cm3When corresponding physics rebound, chemistry rebound and whole
The curve graph to rebound with test point.
Fig. 7 show B material compacted density be 3.45g/cm3When corresponding physics rebound, chemistry rebound and whole
The curve graph to rebound with test point.
Fig. 8 show C-material compacted density be 3.45g/cm3When corresponding physics rebound, chemistry rebound and whole
The curve graph to rebound with test point.
Fig. 9 show D material compacted density be 3.45g/cm3When corresponding physics rebound, chemistry rebound and whole
The curve graph to rebound with test point.
Specific embodiment
The present invention and its advantages are made further specifically below in conjunction with specific embodiment and Figure of description
Bright, still, of the invention is not limited thereto.
Generally speaking, according to the present invention when carrying out the monitoring of positive rebound to lithium ion battery, it is desirable to provide below will
The lithium ion battery for the monitoring being described in detail, and anode is obtained by measuring to the lithium ion battery for monitoring
The parameter of rebound.
Specifically, lithium ion battery according to the present invention needs to increase the disconnected barrier layer of one interlayer of arrangement, the interruption barrier layer
For " barrier " and " no barrier " alternately composition barrier layer, the effect of barrier layer be during charge and discharge prevent lithium from
Son passes through diaphragm, therefore, will not in the corresponding positive and negative anodes pole piece region in part in the interval barrier layer with " barrier "
Electrochemical reaction occurs, so that there is only physics rebounds for the region anode pole piece.
And in the corresponding positive and negative anodes pole piece region in part in the interval barrier layer without " barrier ", it will send out simultaneously
Raw cathode " physics rebound " and " chemistry rebound ", so that the region anode pole piece has physics rebound, chemistry rebound
In order to distinguish physics rebound and chemistry rebound, the present inventor uses interruption barrier layer structure as described above.
Therefore, lithium ion battery of the invention includes anode pole piece, cathode pole piece, diaphragm and interval barrier layer.
It will be described the method for preparing lithium ion battery of the present invention below, first by conventional method in that art to positive and negative electrode foil
Anode and cathode are coated with active material slurry respectively for material two sides.
Positive foil 201 of the invention is usually metallic aluminium or other suitable materials, plays the work of plus plate current-collecting body
With.
The positive electrode active materials slurry being coated on positive foil is by positive active material, positive conductive agent, binder etc.
It mixes.
Positive active material is not particularly limited in the present invention, such as nickle cobalt lithium manganate, cobalt acid lithium, LiFePO 4, manganese
Sour lithium etc. is used equally for the present invention, but not limited to this.
Positive conductive agent is usually conventional conductive agent (such as carbon black, electrically conductive graphite, carbon fiber) and novel conductive agent (such as carbon
Nanotube (CNTs), graphene and its hybrid conductive slurry etc.), can be used for positive conductive agent conductive black SP of the invention,
Electrically conductive graphite KS-6 gas-phase growth of carbon fibre VGCF, carbon nanotubes CNTs, graphene etc., but not limited to this.
Binder is for making ionic conduction agent be capable of forming the coating with certain mechanical strength, and it is living with anode to increase it
Combination between property matter coatings.Binder can be Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTEE), polyimides
(PI), fine (PAN) butadiene-styrene rubber (SBR) of polyacrylic acid (PAA), polypropylene, sodium carboxymethylcellulose (CMC), sodium alginate
(ALG), the mixture of one or more of chitosan (CTS) etc., but not limited to this.
The content of each components such as positive active material, positive conductive agent, binder, those skilled in the art can be according to reality
It needs to be determined that the present invention is not particularly limited.
Positive foil is coated on by the positive electrode active materials slurry that positive active material, positive conductive agent, binder are formed
Positive coat 202a and 202b are formed on 201 two sides, and anode pole piece is consequently formed.
Cathode foil 206 of the invention is usually metallic copper or other suitable materials, plays the work of negative current collector
With.
It is mixed by negative electrode active material, cathode conductive agent, binder etc. in the negative active material slurry of cathode foil coating
It closes.
Contain negative electrode active material, cathode conductive agent, binder etc. in cathode coat 104 (104a, 104b).
Negative electrode active material of the invention is not particularly limited, such as natural graphite cathode, artificial plumbago negative pole, interphase
Carbosphere (MCMB), soft charcoal (such as coke) cathode, hard charcoal cathode, carbon nanotube, graphene, carbon fiber；Other non-Carbon anodes
Material such as silicon substrate and its composite material, nitride cathode, tin-based material, lithium titanate, alloy material etc. are used equally for the present invention, but
It is without being limited thereto.
Cathode conductive agent includes conductive black SP, electrically conductive graphite KS-6, gas-phase growth of carbon fibre VGCF, carbon nanotubes
CNTs, graphene etc., but not limited to this.
Binder includes Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTEE), polyimides (PI), polyacrylic acid
(PAA), fine (PAN) butadiene-styrene rubber (SBR) of polypropylene, sodium carboxymethylcellulose (CMC), sodium alginate (ALG), chitosan
(CTS) one or more of the mixture such as, but not limited to this.
The content of each components such as negative electrode active material, cathode conductive agent, binder, those skilled in the art can be according to reality
It needs to be determined that the present invention is not particularly limited.
Cathode foil is coated on by the negative active material slurry that negative electrode active material, cathode conductive agent, binder are formed
Cathode coat 205a and 205b is formed on 206 two sides, and cathode pole piece is consequently formed.
Diaphragm 204 is mainly that the microporous barrier made of polypropylene (PP), polyethylene (PE) or their copolymer is made.
For being interrupted barrier layer, it can be set and one layer of barrier layer is set in anode pole piece two sides.The barrier layer can
With discontinuously clad anode pole piece, that is, be wound on anode pole piece, and repeat this winding in the distance at interval；Alternatively,
It can discontinuously be arranged between anode pole piece and diaphragm, can also discontinuously be arranged between cathode pole piece and diaphragm.Its mesh
Can prevent lithium ion pass through diaphragm.
Barrier in barrier layer is lithium ion insulation, and electrolyte resistance corrosion, material resistant to high temperature can be selected from insulation
Adhesive tape, insulating film.
For example, the material of insulating tape includes but is not limited to polyethylene (PE) and polyvinyl chloride (PVC), as long as lithium can be obstructed
Ion passes through.
The barrier layer coated in order to prevent influences the rebound of anode pole piece, and the barrier of cladding cannot wrap to obtain tension, need
A reserved fixed gap, to not influence pole piece rebound.
According to one embodiment, as shown in Figure 2 A, be interrupted 203 clad anode pole piece of barrier layer (202a, 201,
202b), that is, interruption barrier layer winds the anode along anode pole piece long axis direction compartment of terrain on the direction perpendicular to the long axis
Pole piece at least one week, A-A section was as shown in Figure 2 B.
Alternatively, according to another embodiment, as shown in Figure 3A, the setting of interruption barrier layer 203 is in diaphragm 204 by anode
The side pole piece (202a, 201,202b), A-A section are as shown in Figure 3B.
Alternatively, as shown in Figure 4 A, the setting of interruption barrier layer 203 leans on cathode in diaphragm 204 according to another embodiment
The side pole piece (205a, 206,205b), A-A section are as shown in Figure 4 B, it should be noted that although the barrier layer of present embodiment
203 settings lean on cathode pole piece side in diaphragm 204, but for ease of understanding, are only to work as anode pole piece, cathode pole piece, resistance in Fig. 4 A, 4B
The schematic diagram of side of the positive electrode barrier when parting and diaphragm are laminated.
When the setting of barrier layer 203 is leaned on by the cathode pole piece side (205a, 206,205b) or setting in diaphragm 204 in diaphragm 204
When the side anode pole piece (202a, 201,202b), which can be in a manner of bonding or other modes are fixed on appointing for diaphragm
Side.
As shown in Fig. 1, the corresponding positive and negative anodes pole piece region in region for being provided with barrier is first area P, not set
The corresponding positive and negative anodes pole piece region in the region of barrier is second area Q.According to above-mentioned defined length, first area P's
The ratio of the length b of length a and second area Q is in other words 1:3~3:1, preferably 1:1, i.e. a=b are hindered by being placed equidistant with
Parting, and the first area and the second area are alternately distributed.
The quantity in the region with barrier and the region without barrier is not particularly limited, as long as manufactured battery is convenient for
It is tested.
The barrier with a thickness of 1~10 micron, be preferably 4~6 microns.
Lithium ion battery is assembled into above-mentioned anode pole piece, cathode pole piece, barrier and diaphragm.As described above, positive
The release of elasticity of materials potential energy on pole piece, on the degradation of Kynoar (PVDF) class binder, swelling and pole piece between substance
Adhesion strength such as changes at the factors, can lead to physics rebound.Define the corresponding cell stack of positive pole zone with barrier layer
Layer part is first area P；
Further, since battery, when charging is put, specifically in the battery lifetime since charging first time, battery is sent out
Raw electrochemical reaction.Definition is " chemistry rebound " with the rebound that chemical reaction occurs.In charge and discharge process, except generation " is changed
Learn rebound " except, " physics rebound " can also occur simultaneously.Here, defining the positive corresponding battery stack in region without barrier
Part is second area Q.The region that second area Q corresponds to cathode is while cathode " physics rebound " and " chemistry rebound " area occurs
Domain, i.e. " region integrally rebounded ".
Wherein, first area P and second area Q is as shown in attached drawing 2A, Fig. 3 A and Fig. 4 A.
In the state that anode pole piece or cathode pole piece are unfolded, the length direction X of electrode plates is defined, pole piece width is defined
Direction Y, and defining pole piece in the thickness direction of the stepped construction of coating is direction Z.
It should be pointed out that each part dimension of attached drawing is only to schematically illustrate, actual proportions are not represented.
The shape of battery is made, and there is no limit for example, can be coiled battery (as shown in Figure 2 C), or be lamination type electric
Pond.Wherein, coiled battery be similar to the present invention shown in, and laminated battery plate be usually be by positive and negative anodes pole piece, every
Film is cut into the size of required size, and anode pole piece, diaphragm, cathode pole piece are then overlapped into small battery core monomer, then by small electricity
Core monomer stacks the one big battery core of composition that is together in parallel.
When coiled battery is made, barrier should not be disposed at the bending part of battery, that is, coiled battery it is curved
It is the second area of the no barrier at folding.
The thickness of the anode pole piece of first area and second area is distinguished after cold pressing process, after first time charging and discharging
D1-1And D2-1, the 5th, 10,15,20,50,100,150,200,400,600,800,1000,1200,1400,1600,1800,
The thickness D of positive foil is measured after 2000 and 2500 circulation technologies respectivelyN- foil, first area and the corresponding anode of second area
The thickness D of pole piece1-nAnd D2-n；Preferably, after first time charging and discharging, 10,20,100,200,400,800 circulation technologies
Carry out these measurements.
In general, in order to obtain credible thickness value, usually using high accuracy number altimeter (model MH-15M, Japan, producer
Nikon) instrument respectively measures the thickness of the above first area and second area, and arrives multiple arithmetic mean of instantaneous value.It is preferred that
Ground takes 3 measurement arithmetic mean of instantaneous values.
Measure the thickness D of positive foilN- foilIt can measure, can also measure after coating before the coating, by
It is negligible relative to the micron-sized thickness of pole piece in the elongation of metal, therefore D is preferably measured before the coatingN- foil。
It is calculated as follows according to institute's measured value: anode pole piece physics rebound rate αN- object；Anode pole piece entirety rebound rate αIt is n- whole；Just
Pole pole piece chemistry rebound rate αN-ization。
αN- object=(D1-n-DN- 0)/(DN- 0-DN- foil) (I)
αIt is n- whole=(D2-n-DN- 0)/(DN- 0-DN- foil) (II)
Anode pole piece chemistry rebound rate αN-izationIt can be obtained by Formula Il I
αN-ization=(D2-n-D1-1)/(D1-1-DN- foil) (III)。
Wherein, DN- foilFor positive foil thickness, DN- 0For anode pole piece thickness after roll-in；
D1-1Headed by when discharging after primary cell charging first area corresponding anode pole piece thickness；
D2-1Headed by primary cell charging after discharge when the corresponding anode pole piece of second area thickness；
D1-nThe thickness of the corresponding anode pole piece in first area when being circulating battery n weeks；
D2-nThe thickness of the corresponding anode pole piece of second area when being circulating battery n weeks.
Wherein, n is as defined above.
To the physics rebound rate α of gained anode pole pieceN- object, anode pole piece whole rebound rate αIt is n- wholeWith the change of anode pole piece
Learn rebound rate αN-izationCurve graph is drawn to the time.
The rebound of lithium ion cell positive thickness is monitored with above method, according to anode pole piece physics rebound rate
αN- object, chemical rebound rate αN-izationAnd/or anode pole piece entirety rebound rate αIt is n- wholeVariation Features to anode pole piece carry out physics, change
And/or the optimization of entirety.
Specifically, while the technology of the present invention integrally rebounds by monitoring anode pole piece, the physics of anode has been distinguished respectively
Rebound and chemistry rebound, can specify material in cyclic process, different physics, chemistry and the evolving trend integrally to rebound；And
And enlightenment can also be played the role of to the reduction of material rebound, such as material feedstock selection, design of material thinking according to test result
Deng；In addition, to different materials rebound size look-ahead, rapid evaluation different materials ballistic properties are excellent in the battery development phase
Bad, guiding material type selecting, the design optimization and material technique for applying for carrying out battery core improves.
Optimize the process of battery design by the following examples to illustrate test device and method according to the present invention.
Embodiment 1
It is prepared as follows lithium ion battery of the invention, in which:
Anode: positive foil is that specification is 0.012 × 666mm metal aluminum foil；Positive coating material are as follows: nickle cobalt lithium manganate three
Metaclass monocrystalline positive electrode A, carbon nanotube (CNTs), conductive agent SP and Kynoar (PVDF) press 96.2:1.2:1.6:
1.0 weight ratios are prepared, compacted density 3.45g/cm3.Wherein, positive coating material dual coating is in positive foil aluminium foil
On.
Diaphragm material are as follows: specification is 12 μ m 88mm polyethylene diagrams.
Electrolyte: LiPF6Concentration is 1.1mol/L, and solvent is diethyl carbonate (DEC), ethylene carbonate (EC), carbonic acid
Methylethyl ester (EMC) contains other various additives electrolyte such as vinylene carbonate (VC), sulfuric acid vinyl ester (DTD).
Cathode: cathode foil is that specification is 0.008 × 225mm copper foil；Cathode coating material are as follows: artificial graphite, SP, butylbenzene
Rubber (SBR) and sodium carboxymethylcellulose (CMC), are prepared by the weight ratio of graphite accounting 96.4%.Pressure after roll-in
Real density is 1.65g/cm3.Wherein, cathode coating material dual coating is on cathode foil copper foil.
Barrier layer is pressed gap length 40cm using PVC insulating tape, above-mentioned anode pole piece is coated in a manner of Fig. 2 C.
It is rolled according to anode, diaphragm, cathode with sequence from the inside to the outside.
After cold pressing process, for the first time discharge after, after the 1st~800 circulation technology use high accuracy number altimeter (type
Number MH-15M, producer Japan Nikon) instrument respectively carries out physical testing region shown in Fig. 2A, cathode pole piece test zone
Thickness test, takes 3~5 thickness values, takes arithmetic average.
By formula calculate cold pressing process after, for the first time discharge after, after the 1st~800 circulation technology electrochemistry rebound,
As a result as shown in Figure 5.
It integrally rebounds with assembly monitor anode pole piece by means of the present invention, meanwhile, distinguish the physics rebound of anode
Rebound with chemistry, specify the anode pole piece of nickeliferous cobalt manganic acid lithium ternary class monocrystalline positive electrode A in cyclic process, not jljl
Reason, chemistry and the evolving trend integrally to rebound it can be concluded that, include three metaclass monocrystalline anode of nickle cobalt lithium manganate by curved measurement
The anode pole piece of materials A is in 3.45g/cm3Under compacted density, physics rebound is slowly increased to 10 circulations, after 10 times recycle, object
Reason rebound rate is still slowly increased, and is maintained at 5% hereinafter, in the interior chemical rebound rate one of 800 circulations after 600 circulations
It is straight slowly to increase, and whole rebound rate is slowly increased to about 18% in 800 circulations.
Embodiment 2
In addition to making the compacted density of three metaclass monocrystalline positive electrode A of nickle cobalt lithium manganate from 3.45g/cm3It is reduced to 2.85g/
cm3Except, to carry out above-mentioned test under conditions of same as Example 1.The corresponding rebound rate of its anode pole piece is followed with charge and discharge
Ring change curve is as shown in Figure 6.
Physics rebound, chemistry rebound and the whole rebound of anode pole piece increase with the increase of cycle-index.Meanwhile area
The physics rebound and chemistry rebound of anode are divided.Compared with the result in embodiment 1, chemistry rebound is substantially unchanged, and physics is anti-
Bullet and whole rebound have certain decline.This is because compacted density becomes smaller, pole piece internal pore is more, and pole intra-piece voids can be held
Receive the rebound of more physics, simultaneously as positive electrode composition is unchanged, therefore under equal conditions chemistry rebound also substantially without
Variation.Therefore, when compacted density reduces, the rebound of anode pole piece can reduce under to a certain degree, this is anode pole piece rebound
Optimization direction provides reference data.
Embodiment 3
In addition to using nickle cobalt lithium manganate ternary polycrystalline cathode material B to replace three metaclass monocrystalline positive electrode A of nickle cobalt lithium manganate
Except, to carry out above-mentioned test under conditions of same as Example 1.Wherein, nickle cobalt lithium manganate ternary polycrystalline cathode material B is logical
Second particle obtained by primary particle (primary particle partial size D50 value is 280nm) compound is crossed, second particle entirety pattern is in
Spherical, material B partial size D50 value is 9.65 μm, and material surface does not do cladding processing.The corresponding rebound rate of its anode pole piece is with filling
Discharge cycles change curve is as shown in Figure 7.
Physics rebound, chemistry rebound and the whole rebound of anode pole piece increase with the increase of cycle-index.Meanwhile area
The physics rebound and chemistry rebound of anode are divided.Compared with the result in embodiment 1, physics rebound is substantially unchanged, and chemistry is anti-
Bullet and whole rebound increase.This is because contain primary particle in second particle material B, and it is primary different in second particle
The rebound of grain is inconsistent, in rebound contraction and expansion process caused by electrochemical reaction in charge and discharge process, it is easier to make
It is broken at second particle, cause chemistry rebound to increase；In view of second particle material has " isotropism " better advantage, needle
To second particle positive electrode, the rebound of anode pole piece can be optimized by the primary particle in optimization second particle material.
Embodiment 4
In addition to use nickle cobalt lithium manganate ternary polycrystalline cathode material C replace nickle cobalt lithium manganate ternary polycrystalline cathode material B it
Outside, to carry out above-mentioned test under conditions of same as Example 3.Wherein, nickle cobalt lithium manganate ternary polycrystalline cathode material C is to pass through
Optimization material B is obtained, and is mainly changed to individual particle of material and grain granulation degree, primary particle partial size D50 value
120nm is down to by 280nm, pattern more tends to spherical, and particle internal flaw is less；It is obtained by an individual particle compound
To second particle, second particle partial size D50 value is 9.82 μm, and material C relative material B primary particle partial size is smaller, two after granulation
Secondary grain diameter is similar, illustrates that material C is higher with respect to granulation degree；In spherical, material surface does not wrap material C entirety pattern
Processing is covered, the corresponding rebound rate of anode pole piece is as shown in Figure 8 with charge and discharge cycles change curve.
As shown in Figure 8, the physics rebound, chemistry rebound and whole rebound of anode pole piece increase with the increase of cycle-index
Greatly.Physics rebound and chemistry rebound are suitable to the contribution integrally to rebound.Meanwhile physics rebound and the chemistry of anode pole piece are distinguished
Rebound.
Compared with the result in embodiment 3, the physics rebound of anode pole piece is substantially without reduction, and chemistry rebound is obviously dropped
Low, this is because the primary particle size in the present embodiment is smaller, it is less that pattern more tends to spherical and particle internal flaw, secondary
Grain granulation degree increases, and material rebounds in charge and discharge process caused by electrochemical reaction in contraction and expansion process, secondary
Particle is non-breakable, meanwhile, material is reduced with respect to " isotropism is good ", material rebound.It therefore, can be in adjustment positive electrode
Primary particle size and aggregate particle size rebound to optimize material.
Embodiment 5
In addition to using AlF3The nickle cobalt lithium manganate ternary polycrystalline cathode material D (its partial size is by 9.72 μm) of cladding replaces nickel
Except cobalt manganic acid lithium ternary polycrystalline cathode material B, to carry out above-mentioned test under conditions of same as Example 3.Its anode pole piece
Corresponding rebound rate it is as shown in Figure 9 with charge and discharge cycles change curve.
Physics rebound, chemistry rebound and the whole rebound of anode pole piece increase with the increase of cycle-index.Meanwhile area
The physics of anode pole piece has been divided to rebound and chemistry rebound.
Compared with the result in embodiment 3, physics rebound is reduced, and chemistry rebound and whole rebound are substantially reduced, this be by
Can be used for stabilizing material structure in coating to nickle cobalt lithium manganate ternary polycrystalline cathode material, cladding as protective layer every
Exhausted electrolyte is directly contacted with positive electrode active materials, dramatically reduces a series of side reactions, meanwhile, it improves hot steady
It is qualitative, to reduce the rebound of material, therefore material rebound can be optimized according to being coated to positive electrode.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (11)
1. a kind of lithium ion battery for the rebound monitoring of lithium ion cell positive thickness, comprising:
Anode pole piece, the anode pole piece include the positive electrode coating arranged on the two sides of positive foil；
Cathode pole piece, the cathode pole piece include the negative electrode material coating arranged on the two sides of cathode foil；With
Diaphragm,
Wherein, the anode pole piece, the cathode pole piece and the diaphragm are arranged as being located at the diaphragm in the positive pole
Between piece and the cathode pole piece,
Wherein, the lithium ion battery further comprises barrier, and the barrier intermittent arrangement is so that the lithium-ion electric
Pond is formed with the first area with the barrier and the second area without the barrier,
Wherein, the barrier is along anode pole piece long axis direction compartment of terrain perpendicular to the square upward around cladding institute of the long axis
It states anode pole piece or the barrier is discontinuously arranged between the anode pole piece and the diaphragm or is discontinuously arranged in
Between the cathode pole piece and the diaphragm.
2. lithium ion battery according to claim 1, wherein the barrier is insulating tape or insulating film.
3. lithium ion battery according to claim 1 or 2, wherein the barrier with a thickness of 1~10 micron, preferably
It is 4~6 microns.
4. the length ratio of lithium ion battery according to claim 1, the first area and second area is 1:3~3:
1, and the first area and the second area are alternately distributed.
5. lithium ion battery according to any one of claims 1 to 4, wherein the lithium ion battery is coiled battery,
It or is laminated battery plate.
6. lithium ion battery according to claim 5, the coiled battery bending place is the second of the no barrier
Region.
The method being monitored 7. a kind of pair of lithium ion cell positive thickness rebounds, wherein the described method comprises the following steps:
To lithium ion battery described in any one of claim 1~6, positive foil in the lithium ion battery is measured respectively
Thickness DN- foil, anode pole piece thickness D after roll-inN- 0, after battery charging for the first time when discharging, the thickness of first area anode pole piece
D1-1, the thickness D of second area anode pole piece2-1, at circulating battery n weeks, first area anode thickness D1-n, second area anode
Thickness D2-n, the n value is 2~2500；With
Rebound rate is calculated, according to measured DN- foil、DN- 0、D1-1、D2-1、D1-n、D2-nAnode pole piece is calculated separately as follows
Physics rebound rate αN- object, anode pole piece entirety rebound rate αIt is n- wholeAnd anode pole piece chemistry rebound rate αN-ization, wherein the anode
Pole piece chemistry rebound rate αN-izationIt is obtained by formula III:
αN- object=(D1-n-DN- 0)/(DN- 0-DN- foil) (I)
αIt is n- whole=(D2-n-DN- 0)/(DN- 0-DN- foil) (II)
αN-ization=(D2-n-D1-1)/(D1-1-DN- foil) (III)。
8. according to the method described in claim 7, the n value is 20~800.
9. method according to claim 7 or 8, wherein with obtained anode pole piece physics rebound rate αN- object, anode pole piece
Whole rebound rate αIt is n- wholeAnd anode pole piece chemistry rebound rate αN-izationIt maps respectively to minute, obtains the corresponding of anode pole piece
Rebound rate is with charge and discharge cycles change curve.
10. the method that a kind of pair of anode slice of lithium ion battery optimizes, comprising the following steps: with according to claim 7~9
Any one of described in method the rebound of lithium ion cell positive thickness is monitored,
According to anode pole piece physics rebound rate αN- object, anode pole piece chemistry rebound rate αN-izationAnd/or anode pole piece entirety rebound rate
αIt is n- wholeWith the Variation Features of charge and discharge cycles number, the physics, chemistry and whole rebound of anode pole piece are monitored.
11. according to the method described in claim 10, passing through physics, chemistry and the knot integrally to rebound of the monitoring anode pole piece
Fruit improves the optimization of material for lithium ion battery, material type selecting, battery design, materials'use technique.
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