CN101877422A - Method for preparing lithium-ion secondary battery - Google Patents
Method for preparing lithium-ion secondary battery Download PDFInfo
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- CN101877422A CN101877422A CN2009101071770A CN200910107177A CN101877422A CN 101877422 A CN101877422 A CN 101877422A CN 2009101071770 A CN2009101071770 A CN 2009101071770A CN 200910107177 A CN200910107177 A CN 200910107177A CN 101877422 A CN101877422 A CN 101877422A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for preparing a lithium-ion secondary battery in order to solve the problem that a porous film in the conventional lithium-ion battery is easy to drop. The method comprises the following step of: preparing a positive plate and a negative plate. The method also comprises the following steps of: a) mixing inorganic filler, aqueous adhesive, additive and solvent to form paste, wherein the additive is one or more of weakly alkaline aqueous solution of amine, aqueous solution of ammonia and salt solution of ammonium, or weakly acid aqueous solution of acid organic compound, and the inorganic filler is one or more inorganic oxides which are not dissolved into the additive; and b) coating the prepared paste on at least one surface of the positive plate and/or the negative plate, and drying the positive plate and/or the negative plate to form a porous film on the surface coated with the paste. The porous film formed by adopting the technical scheme of the invention is difficult in dropping, has good flexibility and is difficult to break during processing such as winding and the like.
Description
[technical field]
The present invention relates to the preparation of lithium rechargeable battery, especially refer to relate in the secondary cell preparation field that forms perforated membrane on the battery pole piece surface.
[background technology]
Lithium rechargeable battery have high-energy-density, high voltage, cycle life height, memory-less effect, an advantages of environment protection, be widely used in fields such as portable electric appts, electric tool at present.Along with making rapid progress of commercial electronic products, people have higher requirement to the capacity of lithium rechargeable battery, useful life, security performance etc.
Lithium rechargeable battery generally includes positive plate, negative plate and places between the two barrier film.Barrier film has completely cut off the electric current between two electrodes, but ion can freely pass through.Yet diaphragm material is polyethylene or polypropylene at present, easily shrinks, melts under hot conditions, causes the both positive and negative polarity contact easily and short circuit, the generation safety problem.
For this reason, have the scheme that forms at least one perforated membrane on the positive plate of lithium ion battery or negative pole or both surfaces now, this perforated membrane can make battery under overheat condition, can be because of the fusing or the thermal contraction of barrier film, and cause the thermal failure of battery, thereby controlled the thermal effect of battery; Therefore make the lithium rechargeable battery that comprises perforated membrane have security performances such as good overcharging resisting performance and anti-stove heat simultaneously.Form in the process of perforated membrane, with an organic solvent disperse inorganic material powder and resinoid bond usually and obtain slurry, again with slurry coating on the surface of positive plate or negative plate, be drying to obtain this perforated membrane.So the battery that makes by prior art easily comes off owing to perforated membrane bond effect difference, still has certain safety problem.
[summary of the invention]
For solving the caducous problem of perforated membrane in the existing lithium ion battery, the invention provides a kind of preparation method of lithium rechargeable battery.
The inventive method comprises the steps: to prepare positive plate, negative plate; Also comprise the steps, a) inorganic filler, aqueous binders, additive and solvent are made slurry; Additive is one or more in the salting liquid of weak alkaline aqueous solution, ammonia spirit or ammonium of amine, or the slightly acidic water solution of acidic organic compound; Described inorganic filler is one or more inorganic oxides that are insoluble to described additive; B) slurry that makes is laid at least one surface of positive plate and/or negative plate, drying makes on the surface that is laid with slurry and forms perforated membrane.
Adopt technical solution of the present invention, owing to adopt aqueous binders and increased additive, make inorganic oxide particles firmly stick to the pole piece surface, the perforated membrane of formation is difficult to come off, and have flexible preferably, cracky not in the courses of processing such as coiling.Additive has improved the dispersiveness of inorganic filler particle in adhesive solution simultaneously, prevents the reunion or the sedimentation of inorganic filler particle.These additives can be removed through super-dry in pole piece manufacturing process, so can not influence battery performance in the later stage owing to have lower boiling point or decomposition temperature simultaneously.
[embodiment]
In order to make technical problem to be solved by this invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Announce the preparation method of lithium rechargeable battery in this embodiment, comprised preparation positive plate, negative plate; A) inorganic filler, aqueous binders, additive and solvent are made slurry; Described additive is one or more in the salting liquid of weak alkaline aqueous solution, ammonia spirit or ammonium of amine, or the slightly acidic water solution of acidic organic compound; Described inorganic filler is one or more inorganic oxides that are insoluble to described additive; B) slurry that makes is laid at least one surface of positive plate and/or negative plate, drying makes on the surface that is laid with slurry and forms perforated membrane.
Wherein, solvent is deionized water or organic solvent, preferably adopts deionized water.Aqueous binders comprises cellulose sodium salt, as sodium carboxymethyl cellulose solution (CMC), also can be the water-based emulsion of butadiene-styrene rubber (SBR), polytetrafluoroethylene (PTFE), polyacrylonitrile etc., preferably carboxymethyl cellulose sodium water solution (CMC) and polyacrylonitrile water-based emulsion.
Described additive is weak acid or alkalescent, and the volatile or decomposition of additive in the process of drying, guarantees thoroughly to remove.The weak alkaline aqueous solution of amine can be selected from one or more the aqueous solution of methylamine, ethamine, propylamine, dimethylamine, trimethylamine, butanediamine.The salting liquid of ammonium can be selected from one or both the aqueous solution in ammonium chloride, the carbonic hydroammonium, can be with the salt solution mix of the weak alkaline aqueous solution and the ammonium of amine among the present invention.The slightly acidic water solution of acidic organic compound can be selected from one or more the aqueous solution of organic carboxyl acid, phenol and phenol derivatives such as formic acid, acetic acid, propionic acid.Generally require its i.e. volatilization or decomposition fully about 200 degrees centigrade, preferably in 150 degrees centigrade of volatilizations or decomposition.Preferred methylamine, ethylamine solution, ammonia spirit, formic acid solution, the acetum of adopting.
The additive that adds makes the pH value of slurries be adjusted in the scope of 3-6 or 7.5-10, to improve the dispersiveness of inorganic filler particle in adhesive solution, prevents the reunion or the sedimentation of inorganic filler particle.Because these additives have lower boiling point or decomposition temperature, in pole piece manufacturing process, can remove, simultaneously so can not influence battery performance in the later stage through heating.
Inorganic filler can be adopted inorganic filler known in those skilled in the art, in the preferred case, inorganic filler is for being insoluble to one or more inorganic oxides of weak base, as one or more of aluminium oxide, zirconia, titanium oxide, silica, chromium oxide, technetium oxide, rheium oxide etc.; Or be insoluble to one or more inorganic oxides of weak acid, as one or more of aluminium oxide, zirconia, titanium oxide, silica, niobium oxide, molybdenum oxide, chromium oxide, tungsten oxide etc.The more preferably Alpha-alumina of stable performance, zirconia, titanium oxide.
In the preferred case, inorganic filler has bigger specific area, and is not dissolved in the organic electrolyte.The specific area of inorganic filler is preferably 1-4000m
2/ g, more preferably 5-50m
2/ g.For the composition more even and easier dispersion of solid particle in the porous rete that makes composition, the median particle diameter d of described inorganic filler
50Be 10-1000nm, preferred median particle diameter d
50Be the mix use of 30-80nm with the 200-600nm particle diameter, granule and oarse-grained mass ratio are 1: 5-1: 30.More preferably granule and oarse-grained mass ratio are 1: 8-1: 10.Because can adopt particle diameter is the inorganic filler combination of varying number level, makes granular size alternate, is convenient to control thickness and pore size in the perforated membrane preparation process.Greatly reduce lithium metal dendritic crystal that negative pole produces in the growing space of electrode surface in charging process, improved the security performance of battery.Simultaneously, these particles have kept higher specific surface area, make electrolyte transmission speed in perforated membrane accelerate.
Step a) mixed in the slurry process, earlier inorganic filler and deionized water are mixed, add additive then, stir, add binding agent in the whipping process and form slurry.
" slurry that makes is laid at least one surface of positive plate and/or negative plate " of foregoing description, for instance, such as can only laying slurry on a surface of a certain positive plate, also can only lay slurry on a surface of a certain negative plate, perhaps only all lay slurry on two surfaces of a certain positive plate, perhaps only all lay slurry on two surfaces of a certain negative plate, perhaps slurry is also laid on the surface at negative plate when slurry is laid on the surface of positive plate, can only lay a surface of positive plate/negative plate during dressing, also can all lay slurry on two surfaces of positive plate/negative plate.Our main purpose emphasis is in the preparation process of this slurry, the position of laying in the preparation perforated membrane can be selected as required, certainly preferably all positive plates or negative plate surface are all laid slurry and are formed perforated membrane, more preferably lay slurry formation perforated membrane at all positive plates and negative plate surface.
Lay methods such as comprising spraying, printing or slurry coating.
During mixing, be benchmark with the quality percentage composition of slurry, the content of described inorganic filler is 5-35%; The content of described aqueous binders is 0.1-5%; Described additive level is 0.5-3%; The content of described solvent is 60-90%.Such as, deionized water, inorganic filler and an amount of additive are mixed by suitable mass ratio, such as, 400: 100: 4, stir, and in whipping process, add binder mixtures (such as the binding agent consumption be the inorganic filler quality 1%), obtain slurry.Then resulting slurry is adopted methods such as spraying, printing or slurry coating to cover at least one surface of battery anode slice and/or negative plate, dry under 80-150 ℃ temperature then, form and be attached to the positive plate of battery and/or the perforated membrane on the negative plate.In order to obtain the interlayer effect of perforated membrane better, in the preferred case, described slurries are coated on the whole surface on the positive plate of battery and/or negative plate two sides, and because therefore the size of negative plate more preferably is coated in these slurries on the whole surface on battery cathode sheet two sides usually greater than the size of positive plate.Under the preferable case, the thickness of the perforated membrane of formation is the 0.5-20 micron, more preferably the 2-7 micron.Wherein the consumption of deionized water has no particular limits, as long as the slurries that mix can be coated on positive plate and/or the negative plate, under the preferable case, total weight with described deionized water, inorganic filler, additive and binding agent is a benchmark, and the mass content of deionized water is 70-85%.
Through above-mentioned explanation, positive plate, barrier film, negative plate prepares successfully, and successful at pole piece surface formation perforated membrane, and the process of subsequent preparation lithium ion battery is known to the public, so follow-up is done simple introduction.
Lithium rechargeable battery of the present invention, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive plate, barrier film, negative plate successively, and comprises that above-mentioned steps is formed on the perforated membrane on the pole piece.
According to lithium rechargeable battery provided by the invention, consisting of of positive plate is conventionally known to one of skill in the art, and in general, positive plate comprises collector and coating and/or is filled in positive electrode on the collector.Described collector is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip.Positive electrode active materials is conventionally known to one of skill in the art, and it comprises positive active material and binding agent, and positive active material can be selected from the positive active material of lithium ion battery routine.As lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, one or more in lithium phosphate molysite and the Li-Ni-Mn-O system.
Anodal kind and content with binding agent is conventionally known to one of skill in the art, for example, described positive pole can be selected from fluorine resin and/or polyolefin compound with binding agent, as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or the butadiene-styrene rubber (SBR) one or more.In general, described anodal content with binding agent is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.
Negative plate adopts known negative plate in this area, promptly contains negative current collector and the negative electrode material layer that is coated on this negative current collector.Anticathode material layer of the present invention has no particular limits, and is the same with prior art, and negative electrode material layer generally includes the conductive agent that negative electrode active material, binding agent and selectivity contain.Described negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example, can be non-graphitized charcoal, graphite or the charcoal that obtains by high-temperature oxydation by polyyne family macromolecule material, also can use other for example material with carbon elements such as pyrolytic carbon, coke, organic polymer sinter, active carbon.The organic polymer sinter can be by the product with gained after sintering such as phenolic resins, epoxy resin and the charing.
Negative material provided by the invention can also optionally contain the common conductive agent that contains in the negative material of prior art.The content of conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the negative material, and the content of conductive agent is generally 0.1-12 weight %.Described conductive agent can be selected from one or more in conductive carbon black, nickel powder, the copper powder.
Negative pole can be selected from the negative pole binding agent of lithium rechargeable battery routine with adhesive, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, described negative pole is the 0.5-8 weight % of negative electrode active material with the content of binding agent, is preferably 2-5 weight %.
The solvent that the present invention is used for positive electrode and negative material can be selected from the conventional solvent that uses in this area, as being selected from N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of positive active material in the slurries be 40-90 weight %, is preferably 50-85 weight %.
The preparation method of positive plate and negative plate can adopt the whole bag of tricks known in the field.
According to lithium rechargeable battery provided by the invention, electrolyte is nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected among lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), hexafluorosilicic acid lithium (LiSiF6), tetraphenyl lithium borate (LiB (C6H5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl4) and fluorocarbon based sulfonic acid lithium (LiC (SO2CF3) 3), LiCH3SO3, the LiN (SO2CF3) 2 one or more such as electrolyte lithium salt.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
According to lithium rechargeable battery provided by the invention, the preparation method of this battery is as well known to those skilled in the art, in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, add electrolyte, sealing obtains lithium rechargeable battery then.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.No longer endure and state.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
1, Zheng Ji preparation
60 gram polyvinylidene fluoride (PVDF) are dissolved in 770 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents make binder solution, then 2000 gram positive active material cobalt acid lithiums (LiCoO2) and 40 gram acetylene black powder are joined in the above-mentioned solution, add 200 gram N-N-methyl-2-2-pyrrolidone N-s (NMP) again, fully mix and make anode sizing agent; This anode sizing agent is coated to equably the two sides of aluminium foil with tensile pulp machine, through 125 ℃ of vacuum and heating dryings 2 hours, roll-in, cut-parts make the positive pole of millimeter (wide) * 83,750 millimeters (length) * 55.5 micron (thick), contain 10 gram positive active material LiCoO2 on the every positive pole.
2, the preparation of negative pole
With 990 gram graphite P15B-CH (the plain NIPPON CARBON of Japanese charcoal CO., LTD buys), 20 gram mass concentration are that 50% butadiene-styrene rubber (SBR) emulsion and 1500 gram water stir and are made into cathode size, evenly be applied to the two sides of Copper Foil with tensile pulp machine, through 125 ℃ of vacuum and heating dryings 1 hour, roll-in, cut-parts make the negative pole of millimeter (wide) * 85,790 millimeters (length) * 57.5 micron (thick), contain 5.1 gram negative electrode active material graphite on the every negative pole.
3, the preparation of perforated membrane
With d50 is that Alpha-alumina 90 grams of 300nm, Alpha-alumina 10 grams and the 600 gram deionized waters that d50 is 50nm mix, adding mass concentration is 25% ammoniacal liquor, 4 grams, the slurry pH value is adjusted to 8.5, dispersion machine with rotating speed 20HZ disperses 20min again, adding 100 gram mass concentration in the whipping process gradually is the 2%CMC aqueous solution, forms the perforated membrane slurry.Coat two surfaces of above-mentioned negative pole then, 90 ℃ of dryings, secondary rolls again, is 4 microns perforated membrane at negative terminal surface formation thickness.
4, the assembling of battery
The above-mentioned positive pole that obtains, the negative pole that applies perforated membrane and the polyethylene barrier film (Celgard company) that thickness is 9 microns are wound into the electrode group of a square lithium ion battery, and this electrode group are included in the rectangular cell aluminum hull of millimeter (wide) * 6,65 millimeters (length) * 34 millimeter (thick).The nominal capacity of this battery (rated capacity) is 1300 MAHs.
's 1: 1: 1 mixed with vinyl carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to weight ratio, and the LiPF6 of 12.7% weight is dissolved in the above-mentioned mixed solvent obtains electrolyte, 5 gram electrolyte are injected above-mentioned rectangular cell aluminum hull, use adhesive plaster temporarily sealing liquid injection hole then, placed 2 days down at 25 ℃, adopt the current charges of 40mA (0.03C) to change in 10 hours then, changing into the back battery capacity is 30% of rated capacity.
Placed 2 days the sealing liquid injection hole down at 45 ℃.Obtain lithium rechargeable battery.
Embodiment 2
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is, the additive agent mixture service quality concentration that configuration preparation perforated membrane slurry is adopted is 20% ethylamine solution, 7 grams, and the pH value of slurry is adjusted to 9.
Embodiment 3
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is, the additive agent mixture service quality concentration that configuration preparation perforated membrane slurry is adopted is 20% acetum, 5 grams, and the pH value of slurry is adjusted to 5.5.
Embodiment 4
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is, it is 50% SBR emulsion (SBR) that the binder mixtures that configuration preparation perforated membrane slurry is adopted uses 4 gram mass concentration.
Embodiment 5
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is that the preparation perforated membrane uses zirconia 90 grams of 300nm, zirconia 10 grams of 50nm to mix as inorganic filler.
Embodiment 6
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is that the aluminium oxide of 300nm is used in the inorganic filler of preparation perforated membrane.
Embodiment 7
This embodiment is used to illustrate the preparation of lithium rechargeable battery provided by the invention.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is that the perforated membrane thickness of preparation is 15 microns.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation of reference lithium rechargeable battery.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is not add additive in perforated membrane pulp preparation process.Perforated membrane is easy to generate bubble and conglomeration, and the coating difficulty is very big, and thickness is uncontrollable below 10 microns.The porous film surface planarization of preparation is relatively poor, and thickness is 15 microns.
Comparative Examples 2
This Comparative Examples is used to illustrate the preparation of reference lithium rechargeable battery.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is, the configuration of perforated membrane slurry uses 600 gram NMP as solvent, and 2 gram PVDF are as binding agent.
This embodiment is used to illustrate the performance test (test result such as table 1) of lithium rechargeable battery
1, the test of battery capacity and cycle performance
To respectively prepare 20 lithium rechargeable batteries according to the method for embodiment 1-7 and the method for Comparative Examples 1-2, carry out the test of battery capacity, respectively record the capability value of 20 batteries according to following method of testing, and calculating mean value.
Assay method is as follows:
Use BK-7024 (a day company is held up in Guangzhou) secondary cell device for detecting performance, under normal temperature (25 ℃) condition, repeat with 1C (1300 milliamperes) constant voltage charge to 4.2 volt, the charging cut-off current is 20 milliamperes; Be discharged to 3.0 volts charge and discharge process again with 1C, write down the discharge capacity of the cell of the loop ends of the 1st time and the 500th time, and be calculated as follows battery capacity surplus ratio and average time attenuation rate:
Battery capacity surplus ratio (%)=(the 500th loop ends capacity/initial capacity) * 100%.
2, high temperature storage
With above-mentioned according to embodiment 1-7 method and each 50 repetition of battery that make of the method for Comparative Examples 1-2 with 1C (1300 milliamperes) constant voltage charge to 4.2 volt, constant voltage charge is to 20 milliamperes in electric current; After the charging, shelved 10 minutes, be discharged to 3.0 volts, record initial capacity C1 with 1C.Then battery is charged to 4.2 volts with 1C again, under 85 ℃ of conditions, store 48 hours.The storage back is discharged to 3.0 volts with 1C, and the residual capacity of record battery is carried out 1C then and discharged and recharged 3 times, with last capacity record capacity C 2, and the calculated capacity recovery rate:
High temperature capacity restoration rate (%)=(C2/C1) * 100%
3, short-circuit test
With above-mentioned method and each 50 on the battery that makes of the method for Comparative Examples 1-2 according to embodiment 1-7, with 1C (1300 milliamperes) constant voltage charge to 4.2 volt, constant voltage charge is to 20 milliamperes in electric current; Battery is put into liquid nitrogen preserved 60 seconds, battery is cooled off rapidly, electrolyte solidifies.Test battery resistance immediately after the taking-up, resistance are promptly thought less than 10000 ohm battery and are short-circuited.
4,150 ℃ of furnace temperature tests
Above-mentioned method and each 20 on the battery that makes of the method for Comparative Examples 1-2 according to embodiment 1-7 lied prostrate with 0.5C (650 milliamperes) constant voltage charge to 4.2, constant voltage charge is to 20 milliamperes in electric current, then battery is put into baking box, be warming up to 150 ℃ with the speed of 5 ℃/min and transfer constant temperature to.Pass through standard: kept 20 minutes for 150 ℃, that battery does not take place is on fire, smolder, explosion phenomenon.
5, lancing test
Above-mentioned method and each 20 on the battery that makes of the method for Comparative Examples 1-2 according to embodiment 1-7 lied prostrate with 0.5C (650 milliamperes) constant voltage charge to 4.2, constant voltage charge thrusts the center of battery fully to 65 milliamperes in electric current with the speed of 40mm/s with the draw point of diameter 5mm.Pass through standard: battery does not have blast, on fire.
Table 1
As can be confirmed from Table 1, adopt aqueous binders configuration pulp preparation perforated membrane, add additive in the slurry and can improve the perforated membrane performance greatly, prepared lithium rechargeable battery has showed good performance in safety test, 150 ℃ of furnace temperature, the percent of pass of lancing test all is 100%, short circuit ratio is 0%, this explanation battery is in crossing thermal environment, polyethylene barrier film micropore is closed, stoped the generation of electrochemical reaction, and when temperature is too high when the polyethylene barrier film being shunk or melting, because the packing material of perforated membrane is an inorganic particle, can not melt in hundreds of even thousands of degrees centigrade, prevented short circuit between the both positive and negative polarity; Or battery is subjected in the outer damage process, and the barrier film breakage causes short circuit, and perforated membrane can prevent the short circuit diffusion effectively and make the overheated generation security incident of battery.Simultaneously, cycle performance, high temperature capacity restoration rate also increase than the battery of the uncoated perforated membrane of negative pole, this may be because perforated membrane is attached on the negative plate surface, has to a certain degree reduced contacting of electrolyte and electrode, has suppressed the decomposition of electrolyte at electrode surface; Also may be that the perforated membrane specific area is big, adsorb harmful material such as HF, the PF3O etc. of generation in the formation process, suppress the decomposition of electrolyte and negative pole solid-state electrolytic solution interfacial film (SEI film).With compare with organic solvent configuration pulp preparation perforated membrane in the Comparative Examples 2, embodiment has better volumetric properties and security performance.
And in perforated membrane slurry layoutprocedure, do not add additive in the Comparative Examples 1, and slight the reunion takes place in inorganic filler particle, and slurry is inhomogeneous, the coating difficulty, can't obtain the perforated membrane that thickness is little, surface compact is smooth, thereby inside battery stress is increased, influence battery performance greatly.Perforated membrane is easy to generate bubble and conglomeration, and the coating difficulty is very big, and thickness is uncontrollable below 10 microns.The porous film surface planarization of preparation is relatively poor, and thickness is 15 microns.
Adopt aqueous binders, inorganic filler and deionized water configuration pulp preparation perforated membrane, can prevent battery short circuit effectively and when barrier film lost efficacy, play completely cut off electric current prevent overheated.Than the oiliness prescription, water paste prepares that perforated membrane greatly reduces preparation cost and to the pollution of environment, material is easy to get, and technology is simple, is very suitable for industry and promotes.
Claims (15)
1. the preparation method of a lithium rechargeable battery comprises the steps: to prepare positive plate, negative plate;
It is characterized in that, also comprise the steps:
A) inorganic filler, aqueous binders, additive and solvent are made slurry; Described additive is one or more in the salting liquid of weak alkaline aqueous solution, ammonia spirit or ammonium of amine, or the slightly acidic water solution of acidic organic compound; Described inorganic filler is one or more inorganic oxides that are insoluble to described additive;
B) slurry that makes is laid at least one surface of positive plate and/or negative plate, drying makes on the surface that is laid with slurry and forms perforated membrane.
2. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that, is benchmark with the quality percentage composition of slurry, and the content of described inorganic filler is 5-35%;
The content of described aqueous binders is 0.1-5%;
Described additive level is 0.5-3%;
The content of described solvent is 60-90%.
3. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that the weak alkaline aqueous solution of described amine is selected from one or more the aqueous solution of methylamine, ethamine, propylamine, dimethylamine, trimethylamine, butanediamine.
4. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that the slightly acidic water solution of described acidic organic compound is selected from one or more the aqueous solution of formic acid, acetic acid, propionic acid, phenol and phenol derivatives.
5. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that the salting liquid of ammonium is one or both the aqueous solution in ammonium chloride, the carbonic hydroammonium.
6. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that described aqueous binders is a kind of of cellulose sodium salt or butadiene-styrene rubber (SBR), polytetrafluoroethylene (PTFE), polyacrylonitrile.
7. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that described solvent is a deionized water.
8. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that described inorganic oxide is selected from one or more of aluminium oxide, zirconia, titanium oxide, silica, niobium oxide, molybdenum oxide, chromium oxide, tungsten oxide.
9. according to the preparation method of the described lithium rechargeable battery of claim 1, it is characterized in that the median particle diameter d of described inorganic filler
50Be 10-1000nm.
10. according to the preparation method of the described lithium rechargeable battery of claim 9, it is characterized in that described inorganic filler is granule median particle diameter d
50Be 30-80nm inorganic oxide and bulky grain median particle diameter d
50Be the mixing of 200-600nm inorganic oxide, granule and oarse-grained mass ratio are 1: 5-1: 30.
11. the preparation method according to the described lithium rechargeable battery of claim 10 is characterized in that, granule and oarse-grained mass ratio are 1: 8-1: 10.
12. the preparation method according to the described lithium rechargeable battery of claim 1 is characterized in that, the pH value of its slurry is in the scope of 3-6 or 7.5-10.
13. the preparation method according to claim 1 or 12 described lithium rechargeable batteries is characterized in that, step a) mixed in the slurry process, earlier inorganic filler and deionized water are mixed, add additive then, stir, add binding agent in the whipping process and form slurry.
14. preparation method according to the described lithium rechargeable battery of claim 1, it is characterized in that, described solvent is a deionized water, described aqueous binders is a cellulose sodium salt, step a) mixed in the slurry process, earlier inorganic filler and deionized water are mixed, add additive then, the pH value that makes its slurry stirs in the scope of 3-6 or 7.5-10, adds binding agent in the whipping process and forms slurry.
15. the preparation method according to the described lithium rechargeable battery of claim 1 is characterized in that, described drying is dry under 80-150 ℃ temperature.
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| JP4649862B2 (en) * | 2004-04-02 | 2011-03-16 | パナソニック株式会社 | Lithium ion secondary battery and manufacturing method thereof |
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