CN101877422B - Method for preparing lithium-ion secondary battery - Google Patents
Method for preparing lithium-ion secondary battery Download PDFInfo
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- CN101877422B CN101877422B CN2009101071770A CN200910107177A CN101877422B CN 101877422 B CN101877422 B CN 101877422B CN 2009101071770 A CN2009101071770 A CN 2009101071770A CN 200910107177 A CN200910107177 A CN 200910107177A CN 101877422 B CN101877422 B CN 101877422B
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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 that high-energy-density, high voltage, cycle life are high, memory-less effect, advantages of environment protection, be widely used at present the fields such as portable electric appts, electric tool.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, easily causes the both positive and negative polarity contact 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 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 simultaneously the security performances such as good overcharging resisting performance and anti-stove heat.Form in the process of perforated membrane, usually with an organic solvent disperse inorganic material powder and resinoid bond and obtain slurry, again with slurry coating on the surface of positive plate or negative plate, be drying to obtain this perforated membrane.The battery that so makes by prior art easily comes off owing to the perforated membrane bond effect is poor, 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 adopting aqueous binders and having 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 reunion or the sedimentation of inorganic filler particle.These additives can be removed through super-dry in pole piece manufacturing process, so can not affect battery performance in the later stage owing to having 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, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
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, such 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 additive is volatile or decompose 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 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 the phenol derivatives such as formic acid, acetic acid, propionic acid.Its i.e. fully volatilization or decomposition about 200 degrees centigrade of General Requirements is 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 to improve the dispersiveness of inorganic filler particle in adhesive solution, prevents reunion or the sedimentation of inorganic filler particle so that the pH value of slurries is adjusted in the scope of 3-6 or 7.5-10.Because these additives have lower boiling point or decomposition temperature, in pole piece manufacturing process, can remove through heating, so can not affect battery performance in the later stage simultaneously.
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, such 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, such 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 larger 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 that makes composition more even and solid particle in the porous rete more easily disperses 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 area, so that electrolyte transmission speed in perforated membrane is accelerated.
A) mix and make in the slurry process in step, first inorganic filler and deionized water are mixed, then add additive, 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, take the quality percentage composition of slurry as benchmark, 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 consumption of binder be the inorganic filler quality 1%), obtain slurry.Then resulting slurry is adopted the methods such as spraying, printing or slurry coating to cover at least one surface of battery anode slice and/or negative plate, then dry under 80-150 ℃ temperature, form and be attached to the positive plate of battery and/or the perforated membrane on the negative plate.In order to obtain better the interlayer effect of perforated membrane, 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, take the total weight of described deionized water, inorganic filler, additive and binding agent as benchmark, the mass content of deionized water is 70-85%.
Through above-mentioned explanation, positive plate, barrier film, negative plate are successfully prepared, and successful form perforated membrane on the pole piece surface, and the process of follow-up preparation lithium ion battery is public domain, therefore does simple introduction for follow-up.
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.Such 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, such 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 % by weight of positive active material, is preferably the 1-5 % by weight.
Negative plate adopts known negative plate in this area, namely 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-graphitic carbon, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other 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 the sintering such as phenolic resins, epoxy resin and the charing.
Negative material provided by the invention can also optionally contain in the negative material of prior art usually contained conductive agent.The content of conductive agent and kind are conventionally known to one of skill in the art, and for example, take negative material as benchmark, the content of conductive agent is generally the 0.1-12 % by 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, such 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 % by weight of negative electrode active material with the content of binding agent, is preferably the 2-5 % by 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 METHYLPYRROLIDONE (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 the 40-90 % by weight, is preferably the 50-85 % by 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 from lithium hexafluoro phosphate (LiPF6) such as electrolyte lithium salt, 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 Lithium (LiC (SO2CF3) 3), LiCH3SO3, among the LiN (SO2CF3) 2 one or more.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), methyl propyl carbonate (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/L, is preferably the 0.8-1.2 mol/L.
According to lithium rechargeable battery provided by the invention, the preparation method of this battery is well known for the person skilled in the art, in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, add electrolyte, then sealing obtains lithium rechargeable battery.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.No longer endure and state.
The below adopts the mode of embodiment that the present invention is described in further detail.
Embodiment 1
This embodiment is used for illustrating the preparation of lithium rechargeable battery provided by the invention.
1, anodal preparation
60 gram polyvinylidene fluoride (PVDF) are dissolved in 770 gram METHYLPYRROLIDONE (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 mentioned solution, add again 200 gram METHYLPYRROLIDONEs (NMP), 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 (Japanese charcoal element NIPPON CARBON 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
Be that Alpha-alumina 90 gram of 300nm, Alpha-alumina 10 grams and the 600 gram deionized waters that d50 is 50nm mix with d50, 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 gradually 100 gram mass concentration in the whipping process is the 2%CMC aqueous solution, forms the perforated membrane slurry.Then coat two surfaces of above-mentioned negative pole, 90 ℃ of dryings, secondary rolls again, is 4 microns perforated membrane at negative terminal surface formation thickness.
4, the assembling of battery
Positive pole obtained above, 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.
Be that 1: 1: 1 ratio is 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, then use adhesive plaster temporarily sealing liquid injection hole, 25 ℃ of lower placements 2 days, then adopt the current charges of 40mA (0.03C) to change in 10 hours, changing into rear battery capacity is 30% of rated capacity.
At 45 ℃ of lower placements 2 days, sealing liquid injection hole.Obtain lithium rechargeable battery.
Embodiment 2
This embodiment is used for illustrating 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 adopts is 20% ethylamine solution, 7 grams, and the pH value of slurry is adjusted to 9.
Embodiment 3
This embodiment is used for illustrating 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 adopts is 20% acetum, 5 grams, and the pH value of slurry is adjusted to 5.5.
Embodiment 4
This embodiment is used for illustrating 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 adopts uses 4 gram mass concentration.
Embodiment 5
This embodiment is used for illustrating 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 for illustrating 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 for illustrating 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 for the preparation of explanation reference lithium rechargeable battery.
Method according to embodiment 1 prepares lithium rechargeable battery, and different is not add additive in perforated membrane slurry preparation process.Perforated membrane easily produces bubble and conglomeration, applies difficulty very large, 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 for the preparation of explanation 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 for the performance test (test result such as table 1) of explanation 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 according to following method of testing, respectively record the capability value of 20 batteries, 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 again 3.0 volts charge and discharge process with 1C, record the discharge capacity of the cell that the circulation of the 1st time and the 500th time finishes, and be calculated as follows battery capacity surplus ratio and average time attenuation rate:
Battery capacity surplus ratio (%)=(the 500th circulation end capacity/initial capacity) * 100%.
2, high temperature storage
Each 50 repetition of battery that the method for above-mentioned method according to embodiment 1-7 and Comparative Examples 1-2 is made are with 1C (1300 milliamperes) constant voltage charge to 4.2 volt, and constant voltage charge is to 20 milliamperes in electric current; After the charging, shelved 10 minutes, be discharged to 3.0 volts with 1C, record initial capacity C1.Then battery is charged to 4.2 volts with 1C again, under 85 ℃ of conditions, store 48 hours.Be discharged to 3.0 volts with 1C after the storage, then the residual capacity of record battery is carried out 1C and is 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
Each 50 on the battery that the method for above-mentioned method according to embodiment 1-7 and Comparative Examples 1-2 is made, 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 namely thought less than 10000 ohm battery and are short-circuited.
4,150 ℃ of furnace temperature tests
Each 20 on the battery that the method for above-mentioned method according to embodiment 1-7 and Comparative Examples 1-2 is made is with 0.5C (650 milliamperes) constant voltage charge to 4.2 volt, 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 occur is on fire, smolder, explosion phenomenon.
5, lancing test
Each 20 on the battery that the method for above-mentioned method according to embodiment 1-7 and Comparative Examples 1-2 is made is with 0.5C (650 milliamperes) constant voltage charge to 4.2 volt, 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 is without blast, on fire.
Table 1
| Embodiment or Comparative Examples | The 1st cyclic discharge capacity (MAH) | Capacity surplus ratio (%) after 500 circulations | High temperature capacity restoration rate (%) | Short circuit ratio (%) | 150 ℃ of furnace temperature test percent of pass (%) | Lancing test percent of pass (%) |
| Embodiment 1 | 1357 | 86.8 | 82.5 | 0 | 100 | 100 |
| Embodiment 2 | 1355 | 85.2 | 81.9 | 0 | 100 | 100 |
| Embodiment 3 | 1351 | 84.6 | 80.3 | 0 | 100 | 100 |
| Embodiment 4 | 1356 | 83.9 | 79.8 | 0 | 100 | 100 |
| Embodiment 5 | 1354 | 86.6 | 80.8 | 0 | 100 | 100 |
| Embodiment 6 | 1358 | 85.3 | 82.6 | 0 | 100 | 100 |
| Embodiment 7 | 1355 | 82.0 | 81.6 | 0 | 100 | 100 |
| Comparative Examples 1 | 1352 | 62.1 | 75.2 | 4 | 65 | 70 |
| Comparative Examples 2 | 1348 | 80.7 | 77.8 | 2 | 95 | 85 |
As can be confirmed from Table 1, adopt aqueous binders configuration slurry to prepare perforated membrane, add additive in the slurry and can greatly improve the perforated membrane performance, 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 excess Temperature shrinks the polyethylene barrier film or melts, because the packing material of perforated membrane is 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 subject in the outer damage process, and the barrier film breakage causes short circuit, and perforated membrane can effectively prevent the short circuit diffusion 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 large, 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 prepare perforated membrane with organic solvent configuration slurry in the Comparative Examples 2 and compare, 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 occurs 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, greatly affect battery performance.Perforated membrane easily produces bubble and conglomeration, applies difficulty very large, 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 to prepare perforated membrane with deionized water configuration slurry, can effectively prevent battery short circuit 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 technique is simple, is very suitable for industry and promotes.
Claims (13)
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;
Wherein, the median particle diameter d of described inorganic filler
50Be 10-1000nm;
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.
2. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, take the quality percentage composition of slurry as benchmark, 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. the preparation method of described lithium rechargeable battery according to claim 1 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. the preparation method of described lithium rechargeable battery according to claim 1 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. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, the salting liquid of ammonium is one or both the aqueous solution in ammonium chloride, the carbonic hydroammonium.
6. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, described aqueous binders is a kind of of cellulose sodium salt or butadiene-styrene rubber (SBR), polytetrafluoroethylene (PTFE), polyacrylonitrile.
7. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, described solvent is deionized water.
8. the preparation method of described lithium rechargeable battery according to claim 1 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. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, granule and oarse-grained mass ratio are 1: 8-1: 10.
10. the preparation method of described lithium rechargeable battery according to claim 1 is characterized in that, the pH value of its slurry is in the scope of 3-6 or 7.5-10.
11. according to claim 1 or the preparation method of 10 described lithium rechargeable batteries, it is characterized in that, a) mix and make in the slurry process in step, first inorganic filler and deionized water are mixed, then add additive, stir, add binding agent in the whipping process and form slurry.
12. the preparation method of described lithium rechargeable battery according to claim 1, it is characterized in that, described solvent is deionized water, described aqueous binders is cellulose sodium salt, a) mixes and makes in the slurry process in step, first inorganic filler and deionized water is mixed, then add additive, make the pH value of its slurry in the scope of 3-6 or 7.5-10, stir, add binding agent in the whipping process and form slurry.
13. the preparation method of described lithium rechargeable battery is characterized in that according to claim 1, described drying is dry under 80-150 ℃ temperature.
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| CN103917370A (en) * | 2011-09-22 | 2014-07-09 | 三菱树脂株式会社 | Method for producing laminated porous film, and laminated porous film |
| KR20130081055A (en) * | 2012-01-06 | 2013-07-16 | 삼성에스디아이 주식회사 | Positive electrode material for lithium battery, positive material prepared from the material, and lithium battery including the positive electrode |
| CN104064728B (en) * | 2013-03-19 | 2017-04-19 | 万向电动汽车有限公司 | High-energy density lithium ion battery positive electrode and preparation method thereof |
| CN109928750A (en) * | 2018-10-15 | 2019-06-25 | 武汉瑞科美新能源有限责任公司 | A kind of high magnification niobium tungsten oxide fast charge electrode material and its preparation method and application |
| CN112216879B (en) * | 2019-07-10 | 2022-05-13 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN111081984A (en) * | 2019-12-31 | 2020-04-28 | 东莞市沃泰通新能源有限公司 | Preparation method of battery slurry and battery slurry |
| CN112652801B (en) * | 2020-12-23 | 2022-03-18 | 深圳市言九电子科技有限公司 | Button battery roll core, preparation method thereof and button battery using same |
| CN113363423A (en) * | 2021-06-02 | 2021-09-07 | 万向一二三股份公司 | Preparation method of low-cost high-energy-density positive plate and preparation method of lithium battery |
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| JP2005294139A (en) * | 2004-04-02 | 2005-10-20 | Matsushita Electric Ind Co Ltd | Lithium-ion secondary battery and its manufacturing method |
| CN1838468A (en) * | 2005-03-25 | 2006-09-27 | 北京大学 | Polymer lithium ion secondary battery and preparation method thereof |
| CN1973389A (en) * | 2004-05-14 | 2007-05-30 | 松下电器产业株式会社 | Lithium-ion secondary battery and its manufacturing method |
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| JP2005294139A (en) * | 2004-04-02 | 2005-10-20 | Matsushita Electric Ind Co Ltd | Lithium-ion secondary battery and its manufacturing method |
| CN1973389A (en) * | 2004-05-14 | 2007-05-30 | 松下电器产业株式会社 | Lithium-ion secondary battery and its manufacturing method |
| CN1838468A (en) * | 2005-03-25 | 2006-09-27 | 北京大学 | Polymer lithium ion secondary battery and preparation method thereof |
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