CN1277329C - Lithium polymer secondary cell, mfg method and device - Google Patents
Lithium polymer secondary cell, mfg method and device Download PDFInfo
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- CN1277329C CN1277329C CNB2003101163436A CN200310116343A CN1277329C CN 1277329 C CN1277329 C CN 1277329C CN B2003101163436 A CNB2003101163436 A CN B2003101163436A CN 200310116343 A CN200310116343 A CN 200310116343A CN 1277329 C CN1277329 C CN 1277329C
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Abstract
Provided is a lithium polymer secondary battery in which superior load characteristics, cycle characteristics, and high energy density are realized, and its manufacturing method and the manufacturing device. This is the manufacturing method of the lithium polymer secondary battery that is composed of a pair of electrodes and a lithium ion conductive gel layer. Concentration of current on the electrodes is prevented by a method that comprises a process in which, after a precursor solution for forming lithium ion conductive gel is impregnated in at least one of the electrodes in a container capable of pressurization, the one electrode is pressurized and made flat and a process in which the lithium ion conductive gel layer is formed on the surface of one of the electrodes by curing the precursor solution.
Description
Technical field
The present invention relates to lighium polymer secondary battery, its manufacture method and manufacturing installation thereof.In detail, the present invention relates to adopt lighium polymer secondary battery, its manufacture method and the manufacturing installation thereof of lithium-ion-conducting polymer.
Background technology
Lithium secondary battery is fully developed as the power supply of mancarried electronic aid because its theoretical energy density is compared very high with other battery and can miniaturization and.But, also pursuing further lightweight, slimming along with the high performance of mancarried electronic aid.In addition, reliability and the fail safe that also gets very frequent recharge discharge cycles at equipment such as pursuing mobile phone.
Lithium secondary battery before this is because adopt electrolyte at dissolving lithium salts in the organic solvent as the electrolyte between the both positive and negative polarity, so in order to keep the external packing of the reliability that in the dead of night waits having been used iron, aluminum hull.Therefore the weight and the thickness of lithium battery all are subjected to the weight of external packing metal-back, the restriction of thickness.
Therefore prevail now and developing the lighium polymer secondary battery that electrolyte does not adopt liquid.Lighium polymer secondary battery adopts lithium ion conductive polymer or lithium-ion-conducting gel as electrolyte.Because be that its encapsulation of solid electrolyte becomes easily, external packing can be used very light thin materials such as lamination aluminium film, can make battery lightweight more, slimming.The attenuate of can in the orientation of not short circuit of inside, trying one's best in addition.
Such lighium polymer secondary battery can obtain by following method.At first, precursor solution in impregnation between positive pole, negative pole and porous matter separator.Then, make its curing, form the lithium-ion-conducting gel, and the lithium-ion-conducting gel is remained on the separator at electrode surface by methods such as heating, ultraviolet irradiations.Be then separator between both positive and negative polarity, integral body is carried out external packing.
It is very difficult making smooth lithium-ion-conducting gel layer in positive pole, negative pole and insulation surface.If the out-of-flatness of lithium-ion-conducting gel layer can easily cause current concentration, the characteristic of generation battery is the problem of the decline of cycle characteristics particularly.If thicken lithium-ion-conducting gel layer in addition in order to guarantee planarization, can produce the decline and the low problem of energy density of part throttle characteristics again as dielectric substrate.
For example disclose positive pole, negative pole, separator and lithium-ion-conducting gel layer in the patent 2001-283915 communique, the impartial comprehensively pressurization of the cell device that protrusion is arranged has been made the method for its miniaturization and high capacity.But this method has incomplete part, produces problems such as current concentration, inner micro-short circuit.This is external before this, and the technology of leveling when pressurizeing for every electrode is introduced also not in detail.
Inventors of the present invention etc. through strict investigation, have found to form at electrode surface the method for even lithium-ion-conducting gel layer, have finally finished the present invention.
Summary of the invention
The present invention is to provide the manufacture method of the lighium polymer secondary battery that constitutes by the lithium-ion-conducting gel layer that forms between pair of electrodes and electrode, this manufacture method has following feature: comprise the electrode at least one side, with containing lithium salts, nonaqueous solvents, polymerizable monomer and polymerization initiator, the precursor solution that is used for forming the lithium-ion-conducting gel after the impregnation, makes the operation of its planarization to side pressurization in the container that can pressurize; With the curing precursor solution, form the operation of lithium-ion-conducting gel layer at a side electrode surface.
According to the present invention, providing produced with said method is lighium polymer secondary battery, has the lithium-ion-conducting gel layer at least one side's electrode surface of pair of electrodes.
In addition according to the present invention, a kind of lighium polymer secondary battery manufacturing installation also is provided, wherein, have concurrently from electrode surface extrude a side electrode, separator and the contained unnecessary precursor solution of the opposing party's electrode mechanism and, state that precursor solution is extruded from the electrode surface mechanism of sealing.
Description of drawings
Fig. 1 is pack electrode mode figure.
Fig. 2 is the pressure method ideograph.
Fig. 3 is battery mode figure.
Fig. 4 is the pressure method ideograph.
Fig. 5 is the pressure method ideograph.
Fig. 6 is the pressure method ideograph.
Fig. 7 has concurrently from electrode surface to extrude unnecessary precursor solution mechanism and the equipment mode figure of direct sealing mechanism after extruding precursor solution.
Fig. 8 is a load performance table of estimating embodiment 1～4, comparative example 1.
Fig. 9 is a periodic performance table of estimating embodiment 1～4, comparative example 1.
Figure 10 is a load performance table of estimating embodiment 7 and 8, comparative example 3.
Embodiment
The lighium polymer secondary battery that manufacture method of the present invention was suitable for is made of pair of electrodes and the lithium-ion-conducting gel layer that forms between electrode.The pair of electrodes here is meant positive pole and negative pole.
The manufacture method of lighium polymer secondary battery of the present invention, be included in the container that can pressurize electrode with at least one side, containing lithium salts, nonaqueous solvents, polymerizable monomer and polymerization initiator, after being used for forming in the precursor solution impregnation of lithium ion conducting gel, side's electrode pressurization makes the operation of its planarization.
At least a side electrode is implemented with the planarization operation that pressurization is carried out.At the electrode surface of having implemented the planarization operation, because formed the lithium-ion-conducting gel layer (the following gel layer that also is called for short) of same thickness, be difficult for causing current concentration, effectively prevented the particularly decline of cycle characteristics of battery behavior.And there is no need the thickness of thickened gel layer in order to ensure planarization, promoted the part throttle characteristics and the energy density of battery.
The planarization operation is preferably implemented two side's electrodes simultaneously.And, when using separator, can behind a side electrode and separator lamination, carry out planarization, also can utilize pressurization that insulation surface is implemented planarization.
The planarization operation can be carried out according to following method.At first in the container that can pressurize, precursor solution is contained be immersed on the layered product of electrode or electrode and separator.Container used herein as long as do not hinder impregnation and pressurization, has no particular limits.Such as, can enumerate the sack that has an opening at least, the chest that can keep impregnation usefulness precursor solution and lid thereof etc.Wherein preferably use the easy to handle sack.As long as the material of sack can keep precursor solution, energy is withstand voltage, also there is no particular limitation.
In addition,, can fully be penetrated into electrode interior, preferably adopt methods such as the method for normal pressure placement in 0～24 hour or the impregnation of reducing pressure, heating impregnation in order to make precursor solution for impregnation.
And, in impregnation in the container of precursor solution, less as far as possible electrode, the gap beyond precursor solution and any separator.The gap can make that too much the planarization operation is insufficient.
The container that can pressurize preferably uses sack from tractable angle.The thickness of sack is preferably in 30～200 microns.Surpass 200 microns sacks self and absorbed and be used for the pressure of planarization, electrode surface is carried out the impartial planarization meeting very difficulty that becomes.Conversely, be less than 30 microns, the physical strength of sack self is very weak probably can to break when planarization, and carrying out planarization more also can be very difficult.
In addition, when electromagnetic waves such as utilizing ultraviolet ray solidified precursor solution, if the thickness of sack surpasses 200 microns, electromagnetic transmitance descended, and can influence polymerization reaction.And at this moment the electromagnetic wave transmitance of sack is big a bit good, is suitable for more than 50%, preferably more than 80%.
The container that electrode, precursor solution and any separator are housed needs planarization.The pressue device that is used for planarization, only with the surface of electrode and any separator is implemented planarization, and to form the gel layer of same thickness in the above just passable, there is no particular limitation.For example, as shown in Figure 2 have container maintaining body and the smooth pressurizing tool (such as the utensil of flatiron shape) that adds pressure surface, container maintaining body shown in Figure 4 and cylinder etc.In addition, also have and shown in Figure 5 have the structure of a pair of cylinder of certain intervals, overlapping two-layer a pair of cylinder shown in Figure 6 also feasible.Also have, the area that adds pressure surface is in order evenly to pressurize better, more preferably greater than the area of electrode.And preferably the width than electrode is big in order to pressurize more equably for the width of cylinder.
Above-mentioned being used in the pressue device of planarization, the suitable cylinder that uses rubber system.Especially be suitable for using the cylinder of a pair of rubber system.Such device can rotate two cylinders simultaneously and exert pressure simultaneously from the two sides to implement planarization to electrode and any insulation surface.
The height that the concavo-convex lower end with recess of rubber system cylinder surface is the upper end of benchmark protuberance is suitable for 1～500 micron.During greater than 500 microns pressurizations, the concavo-convex transcription of cylinder is on electrode and any insulation surface, and it is very difficult that the planarization on surface just becomes.Less than 1 micron when pressurization, cylinder skids on container, and the result makes fully planarization.Relatively Shi Yi concavo-convex scope is 1～100 micron.
If adopt the sack container, the thickness of sack during greater than 200 microns the concavo-convex influence of cylinder to electrode and insulation surface diminish, the concavo-convex easy transcription of cylinder all makes planarization operation difficulty more during less than 30 microns on electrode and any separator.
In addition, pressurization can have the function of extruding unnecessary precursor solution from electrode and any separator simultaneously concurrently.Can omit a necessary link in the battery manufacture process like this.
Specify for example.Fig. 1 (a)～(d) shows is pack into state behind the sack of electrode.Among the figure the 1,4,7, the 9th, sack, the 2, the 5th, separator, the 3, the 8th, anodal, the 6, the 10th, negative pole.Fig. 1 (a) is the sack that the positive pole that covers separator is housed, and Fig. 1 (b) is the sack that the negative pole that covers separator is housed, and Fig. 1 (c) only is equipped with anodal sack, and Fig. 1 (d) is the sack that negative pole only is housed.When making battery, can use Fig. 1 (a) and (b), Fig. 1 (a) and (d), Fig. 1 (c) and combination (b), but in order to promote energy density, preferably use Fig. 1 (a) and (d), Fig. 1 (c) and combination of electrodes (b).In the sack that electrode and separator are housed, inject precursor solution, make the sack planarization, extrude solution not from electrode in case of necessity, sack is sealed with a pair of rubber cylinder.Directly heating or make its curing with electromagnetic waves such as ultraviolet rays.Can carry out planarization to the surface of electrode or electrode and separator in this way.
Behind the precursor solution of not extruding not, seal and to reach more uniform planarization, keep the little gap state that causes beyond electrode, precursor solution and any separator in the precursor solution container that particularly can make impregnation at once.Therefore the surface of control electrode or electrode and separator at an easy rate, it is simple that Working Procedure Controlling also becomes.And the minimizing in uneven thickness of lip-deep gel layer, the even situation of cloth of the energy density of final battery also improves.
The device that seals immediately after this extruding, example can be with reference to device shown in Figure 7.This is to make its planarization to the sack pressurization that electrode and precursor solution are housed, and extrudes the device of precursor solution.In this planarization operation process, the first half of sack stay cylinder on and also electrode and separator when being flattened state later, shut-down operation.The heat sealing machine that can seal sack that is provided with below with cylinder under the state that operation stops, not sandwiching the electrode pair pocket and seals then.This a succession of operation can be finished with an equipment.The pressures partially of this equipment and with the part of heat sealing machine heating is if the position in equipment relatively seals on getting down from horse near just remaining on the state of extruding.In addition, 61 is sacks of packed battery among Fig. 7, the 62nd, and pressurizing tool, the 63rd, heat sealing machine.
This device uses the sack that electrode and separator and precursor solution are housed, and the less state lower sealing of unnecessary precursor solution has been fixed the electrode perimeter part on electrode and separator.Even only residual have a spot of unnecessary precursor solution, because electrode all might move in sack, so be difficult for processing.And very likely cause the inhomogeneous of electrode surface gel layer.
Use this device, easily on electrode and separator at the less state lower sealing of unnecessary precursor solution, the inhomogeneous situation minimizing of gel layer thickness surface on, finally the even situation of cloth of the energy density of battery also improves.
To impregnation behind the container closure of precursor solution, can carry out planarization and press operation with this device.When the container open-ended uses this equipment, can on the cylinder on Fig. 7 top, staying the solution of extruding, pollute cylinder surface and be unfavorable for that operation carries out smoothly.When sealing, use cylinder after extruding, to seal, use the unnecessary liquid of from precursor solution, extruding to remove spot, help operation and carry out smoothly at once at cylinder surface.And easy control electrode or electrode and insulation surface, inhomogeneous minimizing, finally the energy density of battery is inhomogeneous also less.
Follow above-mentioned planarization operation, solidify precursor solution and form gel layer on the surface of electrode or any separator.The gel layer that obtains can be than slimming before this.The gel layer that 0.1～20 μ m is preferably arranged on the electrode particularly preferably is 0.1～10 μ m.When being thicker than 20 μ m, even thickness is neat and well spaced, interelectrode distance increases, and may produce harmful effect to part throttle characteristics.May cause that also energy content of battery density descends.When being thinner than 0.1 μ m, cause that very likely local current is concentrated, can produce the fail safe that dendritic precipitate influences battery.
The side's electrode that obtains is taken out from container and overlap, can obtain lighium polymer secondary battery with the opposing party's electrode of any separator lamination.In addition, the opposing party's electrode with any separator lamination preferably also is the electrode of handling through the foregoing invention method.
When carrying out planarization, the amount of the precursor solution that injects in the container of pack into electrode and separator and precursor solution is very few, can make that the impregnation of electrode and separator is insufficient, and battery performance is produced harmful effect.Too much can not fully carry out planarization again, also cause the increase of precursor solution such as cost of material.
The container that electrode is equipped with in injection is used for forming the precursor solution amount of lithium-ion-conducting gel, and preferably between electrode and separator 1.1～30 of voidage times, 1.1～10 times of amounts are good especially.This be electrode the space system by
The weight of active material in electrode area * thickness of electrode-(real density of active material)/electrode
Try to achieve.When conductive agent and binding agent are arranged in the electrode, the same with the algorithm of active material, ask volume poor of obtaining material all electrodes from the electrode volume, as voidage in the electrode.
In addition, the volume of separator by
The volume of separator-(weight per unit area)/(skeletal density)
Try to achieve.
When trying to achieve 1.1 times of voidage, the precursor solution impregnation in electrode and the separator is insufficient.When adding the precursor solution of the amount that surpasses 30 times of voidages, can not fully pressurize, thickness increases, and the energy density of battery also descends.Insufficient variable thickness of electrode gel layer that makes of pressurizeing in addition causes, to the part throttle characteristics generation harmful effect of battery.And add the solution of 1.1～10 times of amounts, aspect cost and the working procedure duration aspect all be most economical.
Pack into the size of container of electrode is decided by the size of electrode.The size of container and the size of electrode near the time, can reduce unnecessary container area, when fluid injection, also help impregnation.As the container that can pressurize, be tens of to hundreds of microns from complexity and the thickness of electrode of handling as previously mentioned particularly, sack is only.The size of sack, 1～50 millimeter at the two ends of distance electrode when using equipment shown in Figure 7, comprise the residual liquid part of extruding behind the precursor solution, apart from preferably 5～50 millimeters of the electrode tips that produces residual liquid.
The big or small distance electrode two ends of sack are during less than 1 millimeter, solidify behind the precursor solution that cut off between the end of the end of electrode and sack can be very difficult.When using equipment shown in Figure 7,, just be difficult to guarantee to cut off residual liquid part and closure part if extrude behind the precursor solution size apart from the electrode tip sack that produces residual liquid less than 5 millimeters.Even can seal, cut also at electrode tip and sack end during lamination and can compare difficulty.
The size of sack and the size of electrode near the time, can reduce unnecessary sack area, when fluid injection, also help impregnation.The two ends of distance electrode are during greater than 50 millimeters, and the injection rate of precursor solution increases, and strengthened the cost of precursor solution.Preferably the distance electrode two ends remain in 20 millimeters, and the operation during lamination has also become simply.
The structure and the manufacturing process of the lighium polymer secondary battery beyond above-mentioned, there is no particular limitation, can use the structure and the operation of any known.
At first, the electrode anodal, that negative pole constitutes forms arbitrarily on collector body, and the active material of negative or positive electrode is basically with fixing of adhesive.The material of above-mentioned collector body can be aluminium, stainless steel, titanium, copper, nickel etc., but from electrochemical stability, extensibility, and economy consider, be preferably in anodal use aluminium, negative pole copper.As long as the shape of collector body is the electrode formed of active material fixedly, having no particular limits in shape, can be that paper tinsel, sieve aperture, wire netting, bar are tabular, porous body or the shape etc. of on resin film, being applied electronic conductive material.
The active material of negative pole preferably can insert/break away from the material of lithium on electrochemistry as material with carbon element.This is because the insertion of lithium, break away from current potential near the separating out of lithium metal, dissolution potential, can form high energy density cells.Typical example be the particle shape (flakey, bulk, fibrous, must shape, spherical, sized particles shape) natural or Delanium.The Delanium that also can use graphitizations such as spherical carbon particulate, asphaltic residue powder, isotropic pitch powder to obtain.
Relatively good material with carbon element is the graphite particle that is stained with amorphous carbon on the surface.Such graphite particle can be by taking out in petroleum-type mink cell focuses such as coal class mink cell focus that graphite particle is immersed in tar, pitch etc. or heavy oil then, and the temperature heating more than carbonization is decomposed mink cell focus, pulverizes on demand to obtain.Use this graphite particle, the decomposition reaction of the lithium ion conductive polymer that produces at negative pole in the time of can suppressing to charge intentionally, organic electrolyte, lithium salts.Improved discharging and recharging cycle lie thus, also suppressed the gas generation that decomposition reaction causes.
When negative electrode active material used material with carbon element, positive active material was preferably selected for use by Li
a(A)
b(B)
cO
2(here, A is a kind of or two or more in the transition metal.B is one or more the element in the metals such as the nonmetalloid of periodic law Table III B, IVB or VB family and semimetallic elements, alkaline-earth metal, Zn, Cu, Ti.The number range of a, b, c is respectively 0＜a≤1.15,0.85≤b+c≤1.30,0＜c.) the bedded structure composite oxides represented or contain combined oxidation species at least a of spinelle structure.Representational composite oxides have LiCoO
2, LiNiO
2, LiCo
xNi
1-xO
2(0＜x＜1) etc.
When making positive pole, negative pole, can be used in combination the electric conducting material and the active material of chemical stabilizations such as graphite, carbon black, acetylene black, furnace black, carbon fiber, conductive metal oxide in case of necessity, help improving electrical conductivity.
When making positive pole, negative pole, can also use adhesive in case of necessity.Adhesive can be selected the thermoplastic resin that chemical property is stable, can disperse or dissolve and can not be subjected to the organic electrolyte infringement in suitable solution for use.Most resin is all had gained some understanding, such as optionally being dissolved in organic solution N-N-methyl-2-2-pyrrolidone N-(NMP) to the stable Kynoar of organic electrolyte (PVDF).Other spendable thermoplastic resin has acrylonitrile, methacrylonitrile, ethylene fluoride, chlorobutadiene, vinylpyridine and derivative thereof, polymer and copolymers such as vinylidene chloride monomer, ethene, propylene, cyclic diene (as cyclopentadiene, 1, the 3-cyclohexadiene) butadiene-styrene rubber.
Can by active material when needed with conducting material in adhesive resin mixing system cream, with the suitable machine that is coated with lotion is coated on the collector body, makes electrode after the dry pressurization by uniform thickness.The ratio of adhesive will be as far as possible at the necessary amount minimum, and general 1～15% weight is just enough.When using conducting material, the amount of conducting material generally is 2～15% of an active material layer weight.
Each electrode of making like this with coagulate gel and form one.Gel layer is containing the organic electrolyte impregnation of lithium salts or remaining in the ionic conductivity polymeric matrix.Gel layer is by thermal polymerization or photopolymerization the monomer of polymer substrate and mixture (precursor solution) polymerization that contains the organic electrolyte of lithium salts to be made.
Spendable monomer component generally has poly-mystery segment, is polyfunctional at the polymerization position of polymer, can form three-dimensional crosslinking structure.Typical such monomer such as polyethers gather the product of the terminal hydroxyl of mystery with acrylic acid or methacrylic acid (general designation (methyl) acrylic acid) esterification.As everyone knows, polyether polyols is that initator, addition of ethylene oxide or expoxy propane carry out polymerization and obtain with polynary ethanol such as ethylene glycol, glycerol, trimethylolpropanes.Also can react separately or with poly-(methyl) acrylic ester copolymer of monofunctional polyethers polyalcohols with poly-(methyl) acrylate of multifunctional polyethers polyalcohols.
Organic electrolyte is the solution that has dissolved lithium salts in the nonaqueous solvents of non-proton property (polar organic solvent).Lithium salts as solute can be LiClO
4, LiBF
4, LiAsF
6, LiPF
6, LiI, LiBr, LiCF
3SO
3, LiN (SOCF
3)
2, LiN (COF
3)
2, LiC (SO
2CF
3)
3, LiSCN and these combination.
Nonaqueous solvents can be the cyclic carbonates of ethylene carbonate (EC), propene carbonate (PC) etc.; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate linear carbonate classes such as (EMC); Gamma-butyrolacton (GBL); Ester classes such as ester such as methyl propionate, ethyl propionate class; Oxolane and derivative thereof, 1,3-two alkane, 1, ethers such as 2-dimethoxy-ethane, methyl diethyleneglycol diether; Nitrile such as acetonitrile, benzonitrile; Two oxa-s, penta ring and derivative thereof; Sulfolane and derivative thereof; The mixture of these materials.
Negative pole need be suppressed in the gel layer organic electrolyte side reaction with the graphite-like material with carbon element when using the graphite-like material with carbon element as active material.The nonaqueous solvents that is fit to this purpose preferably based on EC, mixes the solvent of sending from PC, GBL, EMC, DEC and DMC etc.Account for the organic electrolyte that has dissolved 3～35% weight lithium salts in 2～25% above-mentioned mixed solutions such as EC weight, even the ionic conduction degree of fully satisfying the demand is also arranged at low temperatures.
Monomer and the cooperation ratio that contains the lithium organic electrolyte, can reach after polymerization mixture and form the lithium-ion-conducting gel electrolyte layer and can fully form organic electrolyte therein and be continuous phase, but cannot separate and separate out at electrolyte in the process for a long time.Reach this point, the Capacity Ratio of monomer and electrolyte should be in 30/70～2/98 scope, and preferably 20/80～2/98.
The maintenance material of gel layer can use the separator of porous matter.Base material can be the film (paper, nonwoven fabrics etc.) of chemical property stable polymer multiple aperture plasma membrane or these polymer fibers in organic electrolyte such as polypropylene, polyethylene, polyester.The air permeability of these separators is at 1～500sec/cm
3And can be when keeping ion-conductive electrolyte under 91: 9～50: 50 the situation in the weight ratio of base material and ion-conductive electrolyte, can obtain the appropriate balance of mechanical strength and ionic conduction degree.
When not using separator, formation gel layer and electrode integrated, only need be pasted together the both positive and negative polarity that gel layer is arranged that obtains according to the invention described above method and get final product in the inboard of gel layer.
When using separator, separator on overlapping on either party's the electrode, the method cast precursor solution according to the invention described above makes its polymerization formation and separator and the incorporate gel layer of electrode then.Itself and the opposing party's attachment of electrodes that forms integrated gel layer with said method are promptly finished together the making of battery.This method is fairly simple, and makes electrode and base material integrated with gel layer.
Precursor solution can simply form gel layer by thermal polymerization and/or photopolymerization (ultraviolet curing).Infiltrated on the above-mentioned electrode when it being solidified after precursor solution, the coating, photopolymerization is special effective method.
Photoepolymerizationinitiater initiater can use free-radical initiator.Particularly the scope of its light absorption wavelength of phosphorous oxides class polymerization initiator is wider than other initator, on the surface that low-yield wavelength absorption band is solidified precursor solution, in the curable deep to precursor solution of high-energy wavelength absorption band.Use this initator,, can be cured to the deep of electrode and separator at electrode or electrode and separator and when leaving the presoma of cross-linking ion conducting polymer.Particularly can fully be cured to the pore inside of porous matter electrode.
Phosphorous oxides class initator preferably (1) 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, (2) two (2,6-dimethoxy benzoyl)-2,4, two (2,4,6-trimethylbenzene the formyl)-phenyl phosphine oxides in 4-trimethyl-amyl group phosphine oxide or (3).
The amount of polymerization initiator can be 100～5000ppm, can produce harmful effect to battery performance but remain in the battery.
Thermal polymerization as causing the heat cross-linking reaction has thermal polymerizations such as diacyl peroxide class, the new class of peroxy esters class t-butyl peroxy, peroxy carbonates class, azo-compound.Wherein best is (1) t-butyl peroxy neodecanoic acid ester, (2) toluoyl benzoyl peroxide, (3) 3,5, and 5-trimethyl acetyl peroxide (4) t-butyl peroxy pivalate.The harmful effect of above-mentioned thermal polymerization contrast ratio properties and cycle performance is less.
The addition that as far as possible reduces thermal polymerization can reduce the reactions such as decomposition of initator when discharging and recharging.But can not fully carry out polymerization reaction, the monomer of possible remained unreacted again very little.So the addition of thermal polymerization, in the total amount to nonaqueous solvents, preferably in the scope of 1～5000ppm, 50～1000ppm is good especially according to monomer and lithium salts.Thermal polymerization can use one or more to mix and use.Can reduce inner unreacted monomer and unreacted initator like this, can reduce harmful effect, can promote the performance of battery battery performance.
In order to prevent Solution Diffusion between positive pole and dielectric substrate or negative pole and dielectric substrate, to improve the tight type of each electrolyte aspect, can handle the surface of electrolyte layers.The formation of the hypothallus of dielectric substrate and inside battery, negative pole internal matrix layer can adopt different structures according to characteristic separately.The kind, concentration of the having or not of formation, additive, the lithium salts of classification, concentration, the electrolyte of polymerization single polymerization monomer etc. are arranged as the difference separately that contains the precursor solution that is immersed in anodal inner and negative pole inside.
For example the polymeric monomer concentration of side of the positive electrode and negative side can be different separately.Particularly adopt the precursor solution higher, can improve load performance than negative pole polymeric monomer concentration at positive pole.
Perhaps, use propene carbonate to prevent the deterioration that causes because of the electrolyte oxidation at positive pole; Use the precursor solution contain ethylene carbonate at negative pole, the reaction that can not produce decomposition etc. can be inserted the disengaging lithium ion expeditiously.The low ethylene carbonate of performance when being intended to negative pole use low temperature in order to promote cryogenic property, the deterioration of battery performance in the time of can preventing low temperature.
In order to promote cycle performance, add low-molecular-weight crosslinking agent carbonic acid five own esters at negative pole, generate surperficial epithelium easily and can improve cycle performance.Can use the precursor solution of different salinity in addition, use the precursor solution higher can improve the load performance of battery than negative pole salinity at positive pole.
The lighium polymer secondary battery that said method is made has had the gel layer that is different from separator between positive pole and negative pole, can carry out homogenization, slimming to the gel layer on the electrode.
The shape of battery can be cylindrical shape, square, sheet shape.External packing can be used metal, the ironed film of aluminium lamination etc.Cylindrical shape or coiling shape battery after positive pole, the polymerization of negative pole difference, are rolled both positive and negative polarity and are sealed then.After sheet anode, the polymerization of negative pole difference, the lamination both positive and negative polarity comes sealed battery to the ironed film of aluminium lamination with hot melt or hot pressing.
Embodiment
Below specify the present invention with embodiment and comparative example, but the present invention is not subjected to the restriction of these examples.When using ultraviolet irradiation in following in addition all embodiment and the comparative example, all usefulness is that maximum output wavelength is the ultraviolet ray of 365nm.
(embodiment 1～5, comparative example)
Anodal making
At LiCoO
2In the powder, mix the conducting material average grain diameter account for the jointing material Kynoar (PVDF) of 7% weight and to account for 5% weight and be 2 microns acetylene black, adding lotion that N-N-methyl-2-2-pyrrolidone N-(NMP) dissolving obtains, to be coated in thickness be on 20 microns the forging and pressing aluminium foil, can obtain positive pole after the dry pressurization.
The making of negative pole
Mix in Delanium to account for the jointing material Kynoar (PVDF) of 9% weight, adding lotion that N-N-methyl-2-2-pyrrolidone N-(NMP) mixed dissolution obtains, to be coated in thickness be on 20 microns the forging and pressing Copper Foil, can obtain negative pole after the dry pressurization.
The modulation of precursor solution
Modulation is LiBF
4The mixed solution (ethylene carbonate containing ratio account for volume 35%) that is dissolved in ethylene carbonate and gamma-butyrolacton reaches the electrolyte of 2M, and this electrolyte and the diacrylate monomer that contains polyethylene glycol oxide and polyoxypropylene copolymer were modulated by weight 95: 5.Dissolve the Photoepolymerizationinitiater initiater 2,4 of 3000ppm then therein, 6-trimethylbenzene formyl phosphine oxide is as the precursor solution of positive pole.Modulation is LiBF
4The mixed solution (ethylene carbonate containing ratio account for volume 35%) that is dissolved in ethylene carbonate and gamma-butyrolacton reaches 1M, and other solution that obtain with the same method of the anodal electrolyte of modulation are as the precursor solution of negative pole.
Making of fluid injection and battery
Positive pole of making 3 and negative pole 10 are put in the sack (1,9).The multiple aperture plasma membrane that before covers separator 2 on anodal 3 makes it be the state shown in Fig. 1 (a).Negative pole 10 former states pack into (Fig. 1 (d)).
In these sacks, inject precursor solution, decompression impregnation, pressurization respectively then.Pressure method can adopt the pattern of Fig. 2 method shown in Figure 2.The 11st, pressurizing tool (as the thing of flatiron), the 12nd, adorned the sack of electrode.The plate of pressurizing tool or discharge electrode all requires surface smoothing.Infiltrate wherein at the electrode precursor solution that makes injection that simultaneously pressurizes with pressurizing tool as Fig. 2.Seal sack after the pressurization, use 200mW/cm
2The ultraviolet irradiation of intensity 20 seconds.
Negative pole and anodal same operation.Positive pole+the separator and the negative pole that obtain like this take out from sack, are clipped in as Fig. 3 between two ironed films of aluminium lamination (external packing), and heating makes it be fused into structure shown in Figure 3, has so just made the sheet battery of embodiment 1.Among Fig. 3,21 o'clock positive electrode collectors, the 22nd, positive pole and polymer dielectric, the 23rd, separator and polymer dielectric, the 24th, negative electrode collector, the 25th, negative pole and polymer dielectric, the 26th, aluminium pressurizing resin film.
Appraisal procedure
Deciding electric current 16mA, to be charged to cell voltage be 4.2V, arrived behind the 4.2V constant-voltage charge 12 hours.Decide electric current during discharge, when 16mA, 80mA, 160mA, discharge into 2.75V respectively.After deciding electric current 80mA then and being charged to cell voltage and reaching 4.2V, constant-voltage charge 12 hours discharges into 2.75V under the 80mA.Circulate so repeatedly 300 times.
2～4 grades of comparative examples 1 of embodiment
Except that the electrode that has injected precursor solution according to the following method pressurization, with above-mentioned the same make embodiment 2～4 and, the battery of comparative example 1.
The pressure method of embodiment 3 as shown in Figure 5.Among Fig. 5, the 41st, the sack of electrode is housed, the 52nd, pressurizing tool (rubber rollers in pairs).Use linear pressure pressurization to make the precursor solution of injection infiltrate wherein one side from the electrode two sides with pressurizing tool with degree.Can extrude precursor solution on electrode and the separator from electrode surface, insulation surface in this way.
The pressure method of embodiment 4 as shown in Figure 6.Among Fig. 6, the 51st, the sack of electrode is housed, the 52nd, pressurizing tool (two paired rubber rollers that link together).Divide two stages with pressurizing tool, use linear pressure pressurization to make the precursor solution of injection infiltrate wherein one side from the electrode two sides with degree.Compare with the method for embodiment 3, can be more fully extrude precursor solution on electrode and the separator from electrode surface, insulation surface.
Under the fluid injection state, do not add and be pressed into battery in the comparative example 1.
The evaluation method of the battery of 2～4 grades of embodiment and comparative example 1 is identical with embodiment 1.
[evaluation]
Fig. 8 has shown the discharge capacity that discharging current records when 16mA, 80mA, 160mA.Discharge capacity is high more, and the load performance of battery is good more.
Embodiment 1 is because have neat and well spaced gel layer at electrode surface, and load performance also is eager to excel than comparative example 1.
Embodiment 2 because to electrode simultaneously carried out pressurization, electrode surface is more smooth, load performance also is eager to excel than embodiment 1.
Embodiment 3 can impose with the linear pressure electrode surface of degree more smooth from the two sides, load performance also is eager to excel than embodiment 2.
Doublely among the embodiment 4 extrude precursor solution with supporting-point roller, electrode surface is more smooth, and load performance also is eager to excel than embodiment 3.
In embodiment 1,2,3,4, the attenuation gradually of the gel layer of electrode surface, thickness are also more even, and load performance promotes.Particularly in embodiment 3,4, can extrude the precursor solution on electrode or the separator from electrode surface, insulation surface, the thin and distribution equably of the gel layer of electrode surface is best cell manufacturing method.
What Fig. 9 showed is the relation of cycle-index and discharge capacity.Discharge capacity is high more, and periodic performance is good more.
Embodiment 1～4 is the thickness of control electrode surface gel layer evenly, and uneven embodiment 1 compares with gel layer, and cycle performance is more outstanding.
Embodiment 5 and 6
[anodal making], [making of negative pole], [modulation of precursor solution] all with embodiment 1 the same carrying out.
[making of fluid injection and battery]
In impregnation after precursor solution seals pocket, carry out planarization and extrude with equipment shown in Figure 7, many sacks seal once more under the state extruding, all the other and the embodiment 3 the same batteries 30 (embodiment 5) that generate.With generating battery 30 (embodiment 6) with embodiment 3 the same methods.
[appraisal procedure]
Deciding electric current 16mA, to be charged to cell voltage be 4.2V, arrived behind the 4.2V constant-voltage charge 12 hours.Decide electric current 80mA and discharge into 2.75V, repeat ten times.Calculate the energy density of battery this moment with battery capacity, average voltage, volume.
As a result, energy density reaches the number of battery cells of 420Wh/1, is 29 in embodiment 5, is 16 in embodiment 6.
From this result as can be seen,, make near electrode, to be difficult to exist unnecessary precursor solution, can allow the thickness of battery little and even keeping extruding to carry out the battery production method that secondary seals under the state.Can reduce the little battery number of energy density like this.And the inconsistent probability of energy content of battery density also reduces.
Embodiment 7 and 8, comparative example 2 and 3
[anodal making], [making of negative pole], [modulation of precursor solution] all with embodiment 1 the same carrying out.
[making of fluid injection and battery]
Positive pole of making 3 and negative pole 10 are packed in the sack (1,9).On anodal 3, cover the separator 2 (Fig. 1 (a)) of multiple aperture plasma membrane before.The negative pole 10 former states sack (Fig. 1 (d)) of packing into.10 millimeters at the two ends of the big or small distance electrode of sack, 40 millimeters apart from the opposing party two ends.
In these bags, import precursor solution.Injection rate is different separately in positive pole sack that adds separator and the sack that negative pole is housed are housed.It all is the multiple of voidage separately.
Table 1
| Positive pole+separator | Negative pole | |
| Comparative example 2 | 1.0 | 1.0 |
| Embodiment 7 | 1.5 | 1.5 |
| Embodiment 8 | 25.0 | 25.0 |
| Comparative example 3 | 31.0 | 31.0 |
Inject the impregnation of reducing pressure behind the precursor solution, pressurization respectively after sack is sealed.Pressure method uses pressurizing tool that electrode is simultaneously pressurizeed precursor solution is infiltrated wherein as shown in Figure 7, the pressurization back with same device to the sack direct sealing after extruding.
The result can see that in comparative example 2, the precursor solution of injection is less, fully impregnation.Other fully impregnations.To these electrodes 200mW/cm
2The ultraviolet irradiation of intensity 20 seconds.
Positive pole+separator that makes like this and negative pole are taken out from sack, be clipped in as Fig. 3 between two ironed films of aluminium lamination (external packing), heating makes it be fused into structure shown in Figure 3, has so just made the sheet battery of embodiment 1.Among Fig. 3,21 o'clock positive electrode collectors, the 22nd, positive pole and polyeletrolyte, the 23rd, separator and polyeletrolyte, the 24th, negative electrode collector, the 25th, negative pole and polyeletrolyte, the 26th, the ironed film of aluminium lamination.
Appraisal procedure
Deciding electric current 16mA, to be charged to cell voltage be 4.2V, arrived behind the 4.2V constant-voltage charge 12 hours.Decide electric current during discharge, when 16mA, 80mA, 160mA, discharge into 2.75V respectively.After deciding electric current 80mA then and being charged to cell voltage and reaching 4.2V, constant-voltage charge 12 hours discharges into 2.75V under the 80mA.Circulate so repeatedly 7 times.Calculate the energy density of battery this moment with battery capacity, average voltage, volume.
Figure 10 is the discharge capacity that records when discharging current is respectively 16mA, 80mA, 160mA, 400mA.Discharge capacity is high more, and the load performance of battery is good more.
Though the load performance of embodiment 7 and 8 is roughly the same, the discharge capacity of comparative example 3 when 160mA, 400mA reduces.This results from the thickness of electrode surface gel layer, illustrates that the precursor solution amount that adds in the container can not be more than 30 times of voidage.
The invention effect
The manufacture method of lighium polymer secondary battery of the present invention has comprised the planarization operation of electrode or electrode and separation layer, can produce the battery that has promoted periodic performance.
The pressurization operation has the function of extruding precursor solution from electrode or electrode and insulation surface concurrently, can produce the lighium polymer secondary battery of good load performance and high-energy-density.
Claims (9)
1. the manufacture method of the lighium polymer secondary battery that constitutes by pair of electrodes and the lithium-ion-conducting gel layer that between electrode, forms, it is characterized in that, comprise electrode at least one side, with containing lithium salts, nonaqueous solvents, polymerizable monomer and polymerization initiator, after the impregnation, pressurization makes the operation of its planarization to the precursor solution that is used for forming the lithium-ion-conducting gel to side's electrode in the container that can pressurize; With the curing precursor solution, form the operation of lithium-ion-conducting gel layer at a side electrode surface.
2. the manufacture method of lighium polymer secondary battery as claimed in claim 1,
Lighium polymer secondary battery has the separator that keeps the lithium-ion-conducting gel layer between pair of electrodes;
The electrode and the separator that comprise lamination one side, electrode and separator to a side, in the container that can pressurize after the impregnation, electrode and separator pressurization to a side make a side the electrode and the operation of separator planarization with the precursor solution that forms the lithium-ion-conducting gel layer;
To the opposing party's electrode, in the container that can pressurize, after the impregnation,, make the operation of its planarization to the pressurization of the opposing party's electrode with the precursor solution that forms the lithium-ion-conducting gel layer; With
Solidify precursor solution, the operation that forms the lithium-ion-conducting gel layer in a side electrode and insulation surface.
3. the manufacture method of lighium polymer secondary battery as claimed in claim 2, wherein, the planarization operation has the operation function that the contained unnecessary precursor solution of a side electrode, separator and the opposing party's electrode is extruded simultaneously concurrently.
4. the manufacture method of lighium polymer secondary battery as claimed in claim 2, wherein, the planarization operation comprises the operation of the state lower sealing container of the contained unnecessary precursor solution of one side's electrode, separator and the opposing party's electrode just having been extruded from electrode surface.
5. the manufacture method of lighium polymer secondary battery as claimed in claim 1 wherein, is carried out the planarization operation with cylinder.
6. the manufacture method of lighium polymer secondary battery as claimed in claim 5, wherein, cylinder surface has 1～500 micron concavo-convex.
7. the manufacture method of lighium polymer secondary battery as claimed in claim 1, wherein, container is that 30～300 microns thickness, the bag of 50% above light transmittance are arranged.
8. with the described method manufacturing of claim 1, there is the lithium-ion-conducting gel layer in the lighium polymer secondary battery that is made of pair of electrodes and the lithium-ion-conducting gel layer that forms between electrode at least one side's of pair of electrodes electrode surface.
9. the manufacturing installation of the lighium polymer secondary battery that uses in the method for claim 4, have concurrently from electrode surface extrude a side electrode, separator and the contained unnecessary precursor solution of the opposing party's electrode mechanism and, in the mechanism of the state lower sealing that precursor solution has just been extruded from electrode surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002335341A JP4188668B2 (en) | 2002-11-19 | 2002-11-19 | Lithium polymer secondary battery, manufacturing method thereof and manufacturing apparatus thereof |
| JP335341/2002 | 2002-11-19 |
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| CN1503397A CN1503397A (en) | 2004-06-09 |
| CN1277329C true CN1277329C (en) | 2006-09-27 |
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| CN (1) | CN1277329C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009081106A (en) * | 2007-09-27 | 2009-04-16 | Central Res Inst Of Electric Power Ind | Nonaqueous electrolyte secondary battery |
| JP5187733B2 (en) * | 2007-12-11 | 2013-04-24 | Ｎｅｃエナジーデバイス株式会社 | Manufacturing method of multilayer secondary battery |
| CN102522560B (en) * | 2011-12-20 | 2014-03-12 | 中国东方电气集团有限公司 | Lithium ion secondary battery and preparation method thereof |
| JP6187468B2 (en) * | 2012-09-28 | 2017-08-30 | 日本ゼオン株式会社 | Slurry for all-solid secondary battery, method for producing electrode for all-solid-state secondary battery, and method for producing electrolyte layer for all-solid-state secondary battery |
| KR101725915B1 (en) * | 2015-01-09 | 2017-04-11 | 주식회사 엘지화학 | Jig Apparatus Comprising Press Bar |
| JP6790545B2 (en) * | 2016-07-21 | 2020-11-25 | 日産自動車株式会社 | Electrode manufacturing method |
| KR102304737B1 (en) * | 2018-05-31 | 2021-09-24 | 주식회사 엘지에너지솔루션 | Method for manufacturing lithium secondary battery |
| JP7131494B2 (en) | 2019-06-18 | 2022-09-06 | トヨタ自動車株式会社 | fuel cell system |
| JP7136016B2 (en) * | 2019-06-18 | 2022-09-13 | トヨタ自動車株式会社 | fuel cell system |
| CN112952215A (en) * | 2021-01-31 | 2021-06-11 | 复旦大学 | Water-based fiber battery and preparation method thereof |
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| JP4188668B2 (en) | 2008-11-26 |
| CN1503397A (en) | 2004-06-09 |
| JP2004171890A (en) | 2004-06-17 |
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