CN103515607A - Negative electrode slurry of lithium ion battery, positive electrode of lithium ion battery prepared by slurry and battery - Google Patents
Negative electrode slurry of lithium ion battery, positive electrode of lithium ion battery prepared by slurry and battery Download PDFInfo
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- CN103515607A CN103515607A CN201210214393.7A CN201210214393A CN103515607A CN 103515607 A CN103515607 A CN 103515607A CN 201210214393 A CN201210214393 A CN 201210214393A CN 103515607 A CN103515607 A CN 103515607A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention provides negative electrode slurry of a lithium ion battery, a positive electrode of the lithium ion battery prepared by using the slurry, and the battery. The negative electrode slurry comprises a negative-electrode active material, a bonding agent, a solvent and a pore-forming agent, wherein the pore-forming agent is selected from one or more in azo-compound and/or sulfonylhydrazine compound. The slurry, the positive electrode and the battery have the advantages that under the condition of guaranteeing no reduction of the compaction density of a negative electrode piece, the porosity of the electrode piece can be increased, the uniformity of pore distribution is increased, the effective area of a liquid phase for conducting lithium ions is improved, the high energy density of the battery is guaranteed, simultaneously the rate capability and the low-temperature performance of the battery are improved and simultaneously the capacity is also improved.
Description
Technical field
The lithium ion battery negative and the lithium ion battery that the present invention relates to a kind of lithium ion battery cathode slurry and adopt cathode size of the present invention to make.
Background technology
Lithium ion battery is now widely used secondary cell, and it has, and specific energy is high, operating voltage is high, self-discharge rate is low, have extended cycle life, the advantage such as pollution-free.Be widely used in the fields such as electric tool, electric automobile, its not only require energy density high, have extended cycle life, high conformity, fail safe is good, cost is low etc., also requires to have high specific power, good high-rate charge-discharge capability.Therefore improving lithium ion battery rate charge-discharge performance applies significant to it.
The diffusion transport of lithium ion in cathode pole piece is to weigh the important performance indexes of battery rate charge-discharge performance quality.Open-cell porosity in cathode pole piece is determining the diffusion transport of lithium ion, porosity is higher, more be conducive to lithium ion and electrolyte to the raising of electrode interior transmission speed, be conducive to lithium ion simultaneously and in negative active core-shell material, embed the increase of deviating from passage and direction, thus make battery specific power high, there is good high-rate charge-discharge capability.But porosity is higher, the bulk density of active material is lower, the energy density of battery is also lower, therefore, lithium ion battery negative electrode conventionally need to be through compressing tablet to improve compacted density, and then improve energy content of battery density, cathode pole piece through compacting, porosity reduces, and the particularly formation of surperficial closed pore, is difficult to active material internal penetration electrolyte, cause lithium ion in electrode, to be difficult to transportation, finally make performance of lithium ion battery deteriorated.
At present, the compacted density of conventional graphite cathode is generally 1.2-1.6g/cm
3porosity is 20%-50%, and porosity distribution is inhomogeneous, the decrement on pole piece surface is large, aperture is little, and closed pore phenomenon is serious, true pole piece surface porosity factor approximately 10%, although the diffusion coefficient of lithium ion in liquid phase is far above the diffusion coefficient in graphite, the surface area of graphite is 10 of effective liquid phase diffusion area
3-10
6doubly, cathode pole piece is thicker, compacting is larger, and difference is larger.Add bottleneck effect, effectively mass transfer in liquid phase area is less, and lithium ion is very approaching in solid phase and liquid phase diffusion impedance.
In the charge and discharge process of battery, when electric current increases, because mass transfer in liquid phase area is little, current density increases sharply, and the impedance that mass transfer in liquid phase produces occupies higher ratio in total impedance, very large on battery charging and discharging impact, and current density is larger, affects larger.When temperature reduces, the viscosity of electrolyte increases fast, and the transfer impedance of lithium ion in hole becomes large, produces seriously polarization.Therefore, the distributing homogeneity in cathode pole piece porosity and hole is restricting multiplying power and the cryogenic property of battery.
Existing have the electrode that discloses a kind of chargeable lithium cell to comprise collector, active material layer, on collector, wherein, active material layer comprises active material, binding agent and pore-creating polymer, wherein, active material is suitable for reversibly carrying out embedding and the de-embedding of lithium ion, when it is made after battery, pore-creating polymer dissolution is in electrolyte solution, thereby in active layer (or electrode active material layers), play the variation that is used for buffer volumes that forms hole, thereby can suppress the expansion of electrode and battery, improve the cycle life characteristics of battery, electrode is applicable to negative pole, the optional free polyalkylene carbonic ether of pore-creating polymer, polyalkylene oxides, poly-alkylsiloxane, polyalkyl acrylate, polyalkyl methacrylate, material in the group of the compositions of mixtures of their copolymer and above-mentioned polymer.But in this technical scheme, pore-creating polymer cannot form perforate efficiently; And pore-creating polymer may be surrounded and cannot contact with electrolyte by active material, in this case, pore-creating polymer not only cannot play the effect of pore-forming, and may affect due to pore-creating polymer residual the performance such as capacity, multiplying power of battery.
Summary of the invention
The present invention is for negative pole porosity when guaranteeing metric density of overcoming the cathode size of prior art and preparing is low and the inhomogeneous particularly top layer of pore size distribution closed pore phenomenon is serious, the battery multiplying power of preparation and the problem of poor performance at low temperatures, provide a kind of and can prepare porosity lithium ion battery cathode slurry high, the particularly negative pole of even pore distribution and the lithium ion battery negative of preparing with this cathode size and battery.
First object of the present invention is to provide a kind of lithium ion battery cathode slurry, comprises negative active core-shell material, binding agent, solvent and pore creating material, and wherein, pore creating material is selected from one or more in azo-compound and/or sulfonyl hydrazines compound.
Second object of the present invention is to provide a kind of lithium ion battery negative, and this negative pole is coated on negative electrode collector by above-mentioned cathode size, and drying, calendering, heat treatment prepare, and wherein, the porosity of negative pole is 20 ~ 50%.
The 3rd object of the present invention is to provide a kind of lithium ion battery, and this battery comprises battery container and is sealed in electrode group and the electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is above-mentioned lithium ion battery negative.
The present inventor surprisingly finds that technical scheme of the present invention is in the situation that guaranteeing that cathode pole piece compacted density does not reduce, can improve the porosity of pole piece, increase even pore distribution, improve the area of the effective conductive lithium ion of liquid phase, when guaranteeing battery high energy metric density, improve high rate performance and the cryogenic property of battery.Cathode size of the present invention is when preparing pole piece, this class pore creating material of azo-compound in cathode size and sulfonyl hydrazines compound can itself be present in cathode pole piece with solid state, and be evenly distributed, in heat treatment process prepared by pole piece, decompose, with gas form, overflow and make its former position of occupying become hole, and, numerous passages that the effusion of gas forms have also guaranteed the open-cell porosity that pole piece is high, and the porous nickel forming distributes, particularly the present invention is by the heat treatment formation of pore creating material and the hole of extraneous UNICOM, it is perforate, further improved the open-cell porosity on pole piece surface, surface pore is abundanter, be conducive to improve lithium ion and electrolyte to electrode interior transmission speed, be conducive to increase lithium ion embeds and deviates from passage and direction simultaneously in negative active core-shell material, thereby make the battery of preparation there is good high-rate charge-discharge capability and cryogenic property.The decomposition temperature of azo-compound and sulfonyl hydrazines compound is low simultaneously, more easily decomposes, and is also difficult for residual, and be difficult for the impact of receptor 1 activity material etc., can not affect other performances of battery, the gas uniform producing during thermal decomposition can cause uniform pore space structure on pole piece.And method of the present invention is simple and easy to realize.
Accompanying drawing explanation
Fig. 1 is that the battery S11 of embodiment 1 preparation is with the voltage-time curve figure of 10C current charges.
Fig. 2 is that the battery DS11 of comparative example 1 preparation is with the voltage-time curve figure of 10C current charges.
Fig. 3 is that the battery DS22 of comparative example 2 preparations is with the voltage-time curve figure of 10C current charges.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of lithium ion battery cathode slurry, comprise negative active core-shell material, binding agent, solvent and pore creating material, wherein, pore creating material is selected from one or more in azo-compound and/or sulfonyl hydrazines compound, in the situation that guaranteeing that cathode pole piece compacted density does not reduce, can improve the porosity of pole piece, increase even pore distribution, improve the area of the effective conductive lithium ion of liquid phase, when guaranteeing battery high energy metric density, improve high rate performance and the cryogenic property of battery.
Preferably, pore creating material is selected from Celogen Az, unifor or 4, one or more in 4'-disulfonyl hydrazide diphenyl ether, the performance of pole piece after the performance of further optimization slurry and heat treatment, can not cause harmful effect etc. to pole piece, and this kind of material more can guarantee the homogeneity of foaming and low residual quantity.
Preferably, the particle average grain diameter of pore creating material is 0.2 ~ 4um, and further preferably the particle average grain diameter of pore creating material is 0.5 ~ 2.5um, further optimizes the pore space structure of pole piece, optimize the energy density of the porosity of pole piece, the aperture of pore-creating and pole piece, further the combination property of preferred battery.
Preferably, the decomposition temperature of pore creating material is 105 ~ 150 ℃, and after decomposing, residual ash content is not higher than 0.5%, and further preferably residue, not higher than 0.2%, easily decomposes low-residual, can not bring harmful effect to pole piece, battery.
Preferably, with respect to the negative active core-shell material of 100 weight portions, the content of described pore creating material is 1 ~ 6 weight portion, and more preferably 2 ~ 4 weight portions are further optimized the porosity of pole piece and the energy density of battery.
The kind of solvent can be adjusted according to the kind of negative active core-shell material and binding agent.Preferably, solvent can be water or water-soluble solvent, azo-compound of the present invention and this type of material of sulfonyl hydrazines compound are not allowed or slightly soluble in water, in slurry, with solid form, exist, apply slurry on collector after, with solid form, be dispersed in the active material layer of negative pole, can bring into play its special performance.Water system slurry when water is made solvent has non-environmental-pollution, low cost and other advantages, is conducive to a large amount of technology and produces.Now, in better situation, binding agent is water system binding agent, and the preferred water system binding agent of the present invention is selected from one or more in polyvinyl fluoride, polyvinyl chloride or butadiene-styrene rubber.
Negative active core-shell material the present invention is restriction not, the various negative active core-shell materials that can be known to the skilled person, and native graphite for example, one or more in Delanium or hard charcoal, wherein, the grain diameter of negative active core-shell material is 5 microns-50 microns.Wherein, ratio the present invention of negative active core-shell material, binding agent and solvent is not particularly limited, can to material concentration, adjust flexibly according to the viscosity of the slurry coating of the composition of battery electrode active material, binding agent and cathode size to be prepared and the requirement of operability, mode is conventionally known to one of skill in the art.In general the total amount of negative active core-shell material of take is benchmark, and the consumption of binding agent is 2 ~ 6wt%, and the consumption of solvent is 110 ~ 150wt%.
Cathode size of the present invention also can comprise that conductive agent, to increase the conductivity of electrode, reduces the internal resistance of cell.Conductive agent the present invention is restriction not, the various conductive agents that can be known to the skilled person, such as conductive black, nickel powder, copper powder etc.The weight of negative active core-shell material of take is benchmark, and the content of described conductive agent is preferably 1 ~ 4 % by weight.
Cathode size of the present invention also can comprise thickener, make the slurries better effects if making, described thickener is the various high molecular polymers that can increase viscosity, one or more in cellulose etherses such as methylcellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), carboxylic propyl methocel (HPMC) and polyacrylamide (PAM), polyvinyl alcohol (PVA) etc., (ok) its kind is conventionally known to one of skill in the art.In general, according to the difference of thickener kind used, the weight of negative active core-shell material of take is benchmark, and the consumption of thickener is preferably 1 ~ 3 % by weight.
Wherein, in lithium ion battery cathode slurry, also can add other property-modifying additives, the present invention is restriction not, design according to actual needs, for example can add dispersant, improve the paintability of slurry, dispersant can be polyvinyl alcohol, tartrate, citrate etc.
Wherein, preparation the present invention of cathode size is restriction not, can be by negative active core-shell material, binding agent, the mixed preparing such as solvent and pore creating material form slurry, the order of mixing and mode the present invention are without specific (special) requirements, as long as they can be mixed, for example binding agent and solvent can be made to mixed solution, by negative active core-shell material, the particles such as pore creating material are mixed into mixture to be added to together in mixed solution and stirs, in better situation, the present invention is specifically as follows thickener is joined in solvent, under the condition of be less than in vacuum degree-0.08MPa, stir and within 2 ~ 4 hours, obtain mixed solution, then by conductive agent, binding agent, negative electrode active material, pore creating materials etc. add in mixed solution, under the condition of be less than in vacuum degree-0.08MPa, fully stir 6 ~ 8 hours, obtain cathode size.
The present invention provides a kind of lithium ion battery negative simultaneously, by above-mentioned cathode size, is coated on negative electrode collector, and drying, calendering, heat treatment prepare, and the porosity of described negative pole is 20 ~ 50%.
Preferably, be less than-0.08MPa of heat treated vacuum degree, temperature is 110 ~ 160 ℃, the preferred heat treated time is 10 ~ 25min, further optimizes pore structure.
Wherein, the various negative electrode collectors that negative electrode collector is known to the skilled person, for example, can be selected from one or more in aluminium foil, Copper Foil, nickel plated steel strip, Punching steel strip.In better situation, be specifically as follows the Copper Foil of 8 ~ 15um.
Wherein, apply, be dried, the step of calendering, the present invention can adopt the technology of well known to a person skilled in the art, preferably, is dried under vacuum condition and carries out at 80 ~ 105 ℃.Calendering can be carried out in roller machine, adopts the conventional rolling condition in this area, and such as 0.5-3.0 MPa, preferably the speed of calendering is 10 ~ 20m/min.
The preparation of negative pole can also comprise other steps, for example, the cut-parts of reprocessing, cut-parts are known to the skilled person, and after heat treatment is complete, according to the negative pole size of prepared battery request, cut, and obtain cathode pole piece.
Preferably, cathode pole piece thickness prepared by the present invention is 90 ~ 150um, and compacted density is 1.20 ~ 1.45g/cm
3.
The present invention also provides a kind of lithium ion battery, comprises battery container and is sealed in electrode group and the electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is above-mentioned lithium ion battery negative.
The present invention to the preparation method of described lithium ion battery without specific (special) requirements, can carry out with reference to prior art, in general, by barrier film, positive pole and negative pole winding are separated to formation electrode group, electrode group is inserted in battery case, added electrolyte, then sealing, wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is conventional amount used.Can obtain lithium ion battery provided by the invention.The conventional steps such as follow-uply also have ageing, change into, does not repeat them here.
Because the present invention only relates to the improvement to prior art lithium ion secondary battery negative pole, therefore other the Nomenclature Composition and Structure of Complexes of lithium rechargeable battery is had no particular limits.For example the positive pole of battery, barrier film and electrolyte are had no particular limits, can use all types of positive poles, barrier film and the electrolyte that can in lithium rechargeable battery, use.Those of ordinary skill in the art can be according to the instruction of prior art, can select easily and prepare positive pole, barrier film and the electrolyte of lithium rechargeable battery of the present invention, and make lithium rechargeable battery of the present invention by described positive pole, negative pole of the present invention, barrier film and electrolyte, do not repeat them here.
Consisting of of described positive pole is conventionally known to one of skill in the art.In general, anodal preparation adopts the technology that well known to a person skilled in the art, for example positive pole comprises anode sizing agent is coated on positive electrode collector, and drying, calendering prepare.Anode sizing agent generally comprises positive active material, conductive agent, anodal binding agent and anodal solvent.
The kind of described positive electrode collector has been conventionally known to one of skill in the art, for example, can be selected from aluminium foil, Copper Foil, Punching steel strip.In the specific embodiment of the present invention, use aluminium foil as positive electrode collector.
The kind of the binding agent in described positive electrode and content are conventionally known to one of skill in the art, and for example fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).In general, according to the difference of adhesive therefor kind, the weight of positive active material of take is benchmark, and the content of binding agent is 0.01-10wt%, is preferably 0.02-5wt%.
The present invention is not particularly limited described positive active material, can be any positive active material that can be purchased in prior art, for example, can adopt all positive active materials that can be purchased, as LiFePO
4, Li
3v
2(PO
4)
3, LiMn
2o
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4f, LiFeO
2; Or ternary system Li
1+al
1-b-cm
bn
co
2, a, b, c represent molal quantity separately, wherein-0.1≤a≤0.2, and 0≤b≤1,0≤c≤1,0≤b+c≤1.0, L, M, N are one or more in Co, Mn, Ni, Al, Mg, Ga, Sc, Ti, V, Cr, Fe, Cu and Zn.
The present invention is not particularly limited described anodal conductive agent, can be the anodal conductive agent of this area routine, such as at least one in acetylene black, conductive carbon black and electrically conductive graphite.Wherein, the weight of positive active material of take is benchmark, and the content of described anodal conductive agent is 0.5-15wt%, is preferably 1-10wt%.
According to the present invention, described barrier film is arranged between positive pole and negative pole, has electrical insulation capability and liquid retainability energy.Described barrier film can be selected from various barrier films used in lithium ion battery, as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Concrete anodal preparation method can be for being prepared into positive electrode slurries with anodal solvent by positive active material, anodal binding agent and conductive agent, the addition of anodal solvent can be adjusted flexibly according to the viscosity of the slurry coating of anodal slurries to be prepared and the requirement of operability, then the anodal slurries that obtain are coated on plus plate current-collecting body, dry compressing tablet, then cut-parts obtain positive pole.When the positive active material of above-mentioned positive electrode composition, anodal binding agent and conductive agent being prepared into positive electrode slurries with solvent, reinforced order is not asked especially.Dry temperature can be 80-150 ℃, and can be 2-10 hour drying time.Method and the condition of calendering are method known in those skilled in the art.Anodal solvent can be various anodal solvent of the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohols.The consumption of anodal solvent can be coated on conducting base anode sizing agent.
Described electrolyte is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Such as electrolyte lithium salt is selected from one or more in lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorocarbon based Sulfonic Lithium.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution, wherein chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other is fluorine-containing, sulfur-bearing or containing at least one in the chain organosilane ester of unsaturated bond, ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other is fluorine-containing, sulfur-bearing or containing at least one in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour, and the concentration of electrolyte is generally 0.1-2.0 and rubs/liter.
To the present invention be described in more detail by embodiment below.
The various raw materials that use in embodiment are the conventional various raw materials that use in this area, all can be by commercially available.
The present embodiment is used for illustrating cathode size of the present invention and lithium ion battery negative and lithium ion battery.
(1) prepare the cathode size of lithium ion battery
Get graphite 100 weight portions, deionized water 130 weight portions, carbon black 2 weight portions, carboxymethyl cellulose (CMC) 2 weight portions, butadiene-styrene rubber (SBR) 4 weight portions, pore creating material Celogen Az (particle diameter 0.5 ~ 2.5um, 110 ℃ of decomposition temperatures, after decomposing, residual ash content is not higher than 0.2%) 3 weight portions.
First will under the condition of CMC and be less than in vacuum degree-0.08MPa of deionized water, stir and within 3 hours, obtain the CMC aqueous solution, then carbon black, SBR, graphite, pore creating material are added in the CMC aqueous solution, under the condition of be less than in vacuum degree-0.08MPa, fully stir 7 hours, obtain cathode size.
(2) prepare the negative pole of lithium ion battery
Cathode size obtained above is coated in to the copper foil surface that thickness is 12um equably, then the Copper Foil that has applied slurry is dried to moisture at 95 ℃.Then pole piece is rolled, rolling velocity is 15m/min.Finally pole piece is heat-treated, be less than-0.08MPa of the vacuum degree of heat-treat condition, temperature is 140 ℃, and baking time is 15min, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 40.48%, finally section, the anode plate for lithium ionic cell sample S1 of grown * wide * thick=491mm * 43.5mm * 120 μ m.
(3) prepare lithium ion cell positive
Take LiFePO4 (LiFePO
4) 1.5kg, and conductive black (CB), polyvinylidene fluoride (PVDF), 1-METHYLPYRROLIDONE (NMP) are according to weight ratio LiFePO
4: CB:PVDF:NMP=100:5:3.5:110 prepares anode sizing agent, after stirring, be coated on the aluminium foil that 12 μ m are thick, then 100 ℃ are dried 10 minutes, then use tablet press machine compressing tablet, finally section, the based lithium-ion battery positive plate of grown * wide * thick=471mm * 42mm * 160um.
(4) prepare lithium ion battery
The lithium ion battery negative that abovementioned steps (2) and (3) are made, anodally stack successively according to the order of positive plate, barrier film, negative plate with the polypropylene screen barrier film of thick 25 μ m, coiling then, makes the pole piece of lithium ion battery.The steel square lithium ion battery shell of this pole piece being put into high 50mm, thick 5mm, wide 34mm, then injects 3.8g electrolyte, and finally sealed battery case is made 053450 lithium ion battery sample S11.Electrolyte is LiPF6/EC+DEC+EMC+DMC system.
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), the amount of pore creating material is 2 weight portions, makes cathode size, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 38.95%, finally section, the anode plate for lithium ionic cell sample S2 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S22.
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), the amount of pore creating material is 4 weight portions, makes cathode size, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 38.80%, finally section, the anode plate for lithium ionic cell sample S3 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S33.
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), the amount of pore creating material is 6 weight portions, makes cathode size, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 40.56%, finally section, the anode plate for lithium ionic cell sample S4 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S44.
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), the particle diameter of pore creating material is 0.2 ~ 1um, makes cathode size, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 38.58%, finally section, the anode plate for lithium ionic cell sample S5 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S55.
Embodiment 6
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), the particle diameter of pore creating material is 2.5 ~ 4um, makes cathode size, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 38.37%, finally section, the anode plate for lithium ionic cell sample S6 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S66.
Embodiment 7
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, in step (1) that different is, pore creating material is unifor, makes cathode size, and heat treatment temperature is 150 ℃, and to obtain thickness be 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 37.76%, finally section, the anode plate for lithium ionic cell sample S7 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S77.
Embodiment 8
According to the method for embodiment 1, prepare cathode size, negative pole, positive pole and lithium ion battery, different is that in step (1), pore creating material is 4,4'-disulfonyl hydrazide diphenyl ether, makes cathode size, in step (2), heat treated temperature is 160 ℃ to obtain thickness is 120um, and compacted density is 1.32g/cm
3, the cathode pole piece that porosity is 36.95%, finally section, the anode plate for lithium ionic cell sample S8 of grown * wide * thick=491mm * 43.5mm * 120 μ m.All the other steps are all identical, make 053450 lithium ion battery S88.
Comparative example 1
With identical cathode size, negative pole, positive pole and the lithium ion battery prepared of method of embodiment 1, different is
(1) preparation of cathode size
Get graphite 100 weight portions, deionized water 130 weight portions, carbon black 2 weight portions, carboxymethyl cellulose (CMC) 2 weight portions, butadiene-styrene rubber (SBR) 4 weight portions, pore creating material polymer poly alkylsiloxane 3 weight portions.
First will under the condition of CMC and be less than in vacuum degree-0.08MPa of deionized water, stir and within 3 hours, obtain the CMC aqueous solution, then carbon black, SBR, graphite, pore creating material are added in the CMC aqueous solution, under the condition of be less than in vacuum degree-0.08MPa, fully stir 7 hours, obtain cathode size.
(2) prepare the negative pole of lithium ion battery
Cathode size obtained above is coated in to the copper foil surface that thickness is 12um equably, then the Copper Foil that has applied slurry is dried to moisture at 95 ℃.Then pole piece is rolled, rolling velocity is 15m/min, and obtaining thickness is 120um, and compacted density is 1.32g/cm
3cathode pole piece, finally section, the anode plate for lithium ionic cell of grown * wide * thick=491mm * 43.5mm * 120 μ m, all the other steps are all identical, make 053450 lithium ion battery DS11, battery standing is disassembled to obtain cathode pole piece sample DS1 after 1 day.
Comparative example 2
With identical cathode size, negative pole, positive pole and the lithium ion battery prepared of method of embodiment 1, different:
(1) in the preparation of cathode size, do not add pore creating material Celogen Az.
(2) prepare in the negative pole of lithium ion battery and do not heat-treat after negative plate calendering, direct slicing, the anode plate for lithium ionic cell DS2 of grown * wide * thick=491mm * 43.5mm * 120 μ m, all the other steps are all identical, make 053450 lithium ion battery DS22.
Performance Detection:
(1) cathode pole piece porosity detects: the open-cell porosity of cathode pole piece sample S1-S8 prepared by the full-automatic mercury injection apparatus test of the Auto pore IV 9500 above-described embodiment 1-8 that uses U.S. Merck & Co., Inc to produce, maximum pressure is the porosity that 30000PSI and same procedure test comparison example 1 are assembled into the cathode pole piece sample DS2 of cathode pole piece sample DS1 after disassembling for standing 1 day after battery and comparative example 2 preparations, and test result is in Table 1.
(2) capacity after battery partial volume:
The forming and capacity dividing system of battery is: the 0.02C 8h that charges, and 0.2C constant-current constant-voltage charging is to 3.6V, cut-off current 20mA; Shelve 10min; 0.5C discharges into 2.0V; Shelve 10min, 0.2C constant current constant voltage is to 3.6V, cut-off current 0.02C; Shelve 10min; 0.2C discharges into 2.0V, records discharge capacity.The results are shown in Table 1.
Table 1
| Cathode pole piece | Porosity/% | Battery | Capacity/mAh |
| S1 | 40.48 | S11 | 650 |
| S2 | 38.95 | S22 | 646 |
| S3 | 38.80 | S33 | 645 |
| S4 | 40.56 | S44 | 636 |
| S5 | 38.58 | S55 | 638 |
| S6 | 38.37 | S66 | 639 |
| S7 | 37.76 | S77 | 637 |
| S8 | 36.95 | S88 | 633 |
| DS1 | 30.47 | DS11 | 630 |
| DS2 | 28.85 | DS22 | 625 |
。
The porosity of cathode pole piece prepared by embodiments of the invention is high, substantially be more than 36%, and pore-creating after calendering, the pore size distribution of pole piece is even, there is not closed pore in top layer particularly, and pore structure is abundanter, and the capacity of the battery prepared of the present invention is higher, may be due to the raising of open-cell porosity, the formation of SEI film is more fully with stable.
(3) battery low temperature high rate performance test under-20 ℃ of conditions:
The battery S11-S88 under-20 ℃ of conditions being prepared by embodiment 1-8 and comparative example 1-2 and DS11-DS22 respectively with 0.2C, 1C, 2C constant current charge to 3.8V, rear 0.5C is discharged to 1.5V, records charging capacity, in charging, presses, test result is in Table 2.
Table 2
Wherein, DS22 battery is during with 1C current charges, middle pressure is 3.725V, after having charged, normal temperature shelf 24 hours, 0.5C discharge platform 3.4V, far above this battery partial volume platform (the discharge platform 3.241V of 0.5C) at normal temperatures, normal temperature capacity restoration is 120mAh, dissects and finds to analyse lithium, illustrates that battery damages.
The battery S11-S88 under-20 ℃ of conditions being prepared by embodiment 1-8 and comparative example 1-2 and DS11-DS22 respectively with 0.5C constant-current constant-voltage charging to 3.8V, cut-off current 20mA, rear respectively with 0.2C, 1C, 2C constant-current discharge 1.5V, record discharge capacity, in electric discharge, press, test result is in Table 3.
Table 3
(4) normal temperature battery high rate performance test:
The battery S11-S88 at 25 ℃ being prepared by embodiment 1-8 and comparative example 1-2 and DS11-DS22 respectively with 0.2C, 1C, 5C, 10C constant current charge to 3.6V, rear 0.5C is discharged to 2.0V, records charging capacity, in charging, presses, test result is in Table 4.
Table 4
Wherein, DS11, DS22 are without platform (middle pressure) during with 10C current charges, and voltage directly rises to cut-ff voltage, press in now unmatchfully than meaning, and charging curve is shown in Fig. 1, Fig. 2.
The battery S11-S88 under 25 ℃ of conditions being prepared by embodiment 1-8 and comparative example 1-2 and DS11-DS22 respectively with 0.5C constant-current constant-voltage charging to 3.6V, cut-off current 20mA, rear respectively with 0.2C, 1C, 5C, 10C constant-current discharge 2.0V, record discharge capacity, in electric discharge, press, test result is in Table 5.
Table 5
From test result, can find out, battery capacity prepared by cathode pole piece of the present invention is high, low temperature, normal temperature high rate performance excellence.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (16)
1. a lithium ion battery cathode slurry, is characterized in that, comprises negative active core-shell material, binding agent, solvent and pore creating material, and described pore creating material is selected from one or more in azo-compound and/or sulfonyl hydrazines compound.
2. cathode size according to claim 1, is characterized in that, described pore creating material is selected from one or more in Celogen Az, unifor or 4,4'-disulfonyl hydrazide diphenyl ether.
3. cathode size according to claim 1, is characterized in that, the particle average grain diameter of described pore creating material is 0.2 ~ 4um.
4. cathode size according to claim 3, is characterized in that, the particle average grain diameter of described pore creating material is 0.5 ~ 2.5um.
5. cathode size according to claim 1, is characterized in that, the decomposition temperature of described pore creating material is 105 ~ 150 ℃, and after decomposing, residual ash content is not higher than 0.5%.
6. cathode size according to claim 1, is characterized in that, with respect to the negative active core-shell material of 100 weight portions, the content of described pore creating material is 1 ~ 6 weight portion.
7. cathode size according to claim 6, is characterized in that, with respect to the negative active core-shell material of 100 weight portions, the content of described pore creating material is 2 ~ 4 weight portions.
8. cathode size according to claim 1, is characterized in that, described solvent is water; Described binding agent is water system binding agent.
9. cathode size according to claim 8, is characterized in that, described water system binding agent is selected from one or more in polyvinyl fluoride, polyvinyl chloride or butadiene-styrene rubber.
10. cathode size according to claim 1, is characterized in that, described negative active core-shell material is native graphite, one or more in Delanium or hard charcoal, and described cathode size also comprises conductive agent and/or thickener.
11. 1 kinds of lithium ion battery negatives, it is characterized in that, described negative pole is coated on negative electrode collector by cathode size, and drying, calendering, heat treatment prepare, the porosity of described negative pole is 20 ~ 50%, and described cathode size is the cathode size described in claim 1-10 any one.
12. negative poles according to claim 11, is characterized in that, described be less than-0.08MPa of heat treated vacuum degree, and described heat treated temperature is 110 ~ 160 ℃.
13. negative poles according to claim 11, is characterized in that, the described heat treated time is 10 ~ 25min.
14. negative poles according to claim 11, is characterized in that, described dry temperature is 80 ~ 105 ℃, and the speed of described calendering is 10 ~ 20m/min.
15. negative poles according to claim 11, is characterized in that, the compacted density of described negative pole is 1.20 ~ 1.45g/cm
3.
16. 1 kinds of lithium ion batteries, is characterized in that, comprise battery container and are sealed in electrode group and the electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is the lithium ion battery negative described in claim 11-15 any one.
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