CN101604767A - Electrode assemblie and comprise the secondary cell of this electrode assemblie - Google Patents
Electrode assemblie and comprise the secondary cell of this electrode assemblie Download PDFInfo
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- CN101604767A CN101604767A CNA2009101457545A CN200910145754A CN101604767A CN 101604767 A CN101604767 A CN 101604767A CN A2009101457545 A CNA2009101457545 A CN A2009101457545A CN 200910145754 A CN200910145754 A CN 200910145754A CN 101604767 A CN101604767 A CN 101604767A
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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 present invention relates to a kind of secondary cell that is used for the electrode assemblie of battery and comprises this electrode assemblie.Described electrode assemblie comprises positive pole with anode active material layer and the negative pole with anode active material layer.Described assembly further comprises having the porous layer that formed by ceramic material and binding agent and the dividing plate of polyolefin resin layer.Described porous layer has the thickness of about 4～6 μ m and the thickness that described polyolefin resin layer has about 12～16 μ m.
Description
Technical field
The present invention relates to a kind of electrode assemblie and comprise the secondary cell of this electrode assemblie, more specifically, relate to and a kind ofly can make the battery security maximization and do not reduce the secondary cell of battery performance.
Background technology
In recent years, the fast development of small and light mobile electronic device has produced the demand that increases day by day to high power capacity, small size battery.Particularly lithium rechargeable battery can provide the operating voltage at least about 3.6V, this voltage exceeds about 3 times of the nickel-cadmium cell that is widely used in the mobile electronic device or Ni-MH battery, and lithium rechargeable battery has than nickel-cadmium cell or the higher Unit Weight energy density of Ni-MH battery.For above-mentioned reasons, improve research rapidly to lithium rechargeable battery.
In lithium rechargeable battery, the redox reaction that takes place during owing to and negative pole anodal in lithium ion embedding/de-embedding produces electric energy.The manufacturing of lithium rechargeable battery comprise use can reversibly embed/material of de-embedding lithium ion fills organic bath or polymer dielectric as the active material of positive pole and negative pole and between positive pole and negative pole.
Above-mentioned lithium rechargeable battery comprises electrode assemblie, be used for hold electrodes assembly and electrolytical jar and be installed in cap assemblies on the jar, and in electrode assemblie, negative plate and positive plate and the dividing plate that inserts between them are for example reeled with the form of film.
Usually, will be by at least a single or multiple lift TPO microporous polymer layer that forms in polypropylene (PP) and the polyethylene (PE) as dividing plate.But, owing to be sheet or membranaceous as the TPO microporous polymer layer of dividing plate, when internal short-circuit or overcharge and produce when hot, may blocked hole, and also film type separator may be shunk.
Therefore, when the heat that produces in because of lithium rechargeable battery when film type separator was shunk, positive pole and negative pole that the dividing plate after causing shrinking is not isolated partly were in contact with one another, thus cause catch fire, explosion or blast.
In order to remedy the above-mentioned weakness of film type separator, the porous layer that is combined to form that uses binding agent and ceramic material is formed ceramic separator carried out big quantity research, ceramic material for example is silicon dioxide (SiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2) or titanium oxide (TiO
2).
In this case, ceramic separator can remedy fusing and the contraction of membranous type polyolefin separator under about 120 ℃ or higher high temperature.Therefore, the conventional film type separator and the growth trend of ceramic separator have appearred using simultaneously.
But, when using film type separator and ceramic separator simultaneously, improved battery security, but in order to obtain the battery capacity identical with conventional secondary cell, film type separator must be the same with ceramic separator thin.
Particularly, when ceramic layer has predetermined thickness or when thinner, does not improve the fail safe of ceramic layer, and when ceramic layer surpasses predetermined thickness, the battery performance variation.In addition, when film type separator is lower than predetermined thickness, the thermal characteristics variation of secondary cell, and when film type separator is too thick, the battery performance variation.
Therefore, consider the compatibility between film type separator and the ceramic separator, need the optimal design lithium rechargeable battery, make battery security maximization and do not reduce battery performance.
Summary of the invention
The invention provides and a kind ofly can make battery security maximization and do not reduce the secondary cell of battery performance.
Equally, the present invention also provides a kind of capability retention, heat to expose the secondary cell of characteristic and mechanical stability excellence.
According to an aspect of the present invention, electrode assemblie comprises two battery lead plates and the dividing plate that is used to two battery lead plates are isolated mutually.Described dividing plate comprises porous layer that is combined to form and the polyolefin resin layer by ceramic material and binding agent.And described porous layer has the thickness of about 4～6 μ m, and described polyolefin resin layer has the thickness of about 12～16 μ m.
According to a further aspect of the present invention, electrode assemblie comprises: the positive pole that comprises anode active material layer; The negative pole that comprises anode active material layer; And be used to make dividing plate anodal and that negative pole is isolated mutually.Described dividing plate comprises porous layer that is combined to form and the polyolefin resin layer by ceramic material and binding agent.And described porous layer has the thickness of about 4～6 μ m, and described polyolefin resin layer has the thickness of about 12～16 μ m.
According to a further aspect of the invention, secondary cell comprises electrode assemblie and electrolyte, and described electrode assemblie comprises positive pole with anode active material layer, have the negative pole of anode active material layer and be used to dividing plate that positive pole and negative pole are isolated mutually.Described dividing plate comprises porous layer that is combined to form and the polyolefin resin layer by ceramic material and binding agent.And described porous layer has the thickness of about 4～6 μ m, and described polyolefin resin layer has the thickness of about 12～16 μ m.
Described polyolefin resin layer can comprise three layers of polyethylene (PE) individual layer, polypropylene (PP) individual layer or PP-PE-PP.
Described ceramic material can comprise and being selected from by silicon dioxide (SiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2) and titanium oxide (TiO
2) at least a in the group that constitutes.
Described binding agent can comprise the synthetic rubber latex binder or have the acrylic rubber binding agent of cross-linked structure.
Described dividing plate can be arranged on the positive pole with anode active material layer and at least one electrode that has in the anode active material layer negative pole.
In described dividing plate, described porous layer can be coated on anode active material layer or the anode active material layer, and described polyolefin resin layer can be arranged on the described porous layer.
Perhaps, in described dividing plate, described polyolefin resin layer can be arranged on anode active material layer or the anode active material layer, and described porous layer can be coated on the described polyolefin resin layer.
Description of drawings
Fig. 1 is the exploded view of a battery component execution mode; And
Fig. 2 A and 2B are the sectional views of the battery component of Fig. 1, are used to illustrate electrode assemblie and carrier ring.
Embodiment
Now describe the present invention in detail with reference to illustrative embodiments of the present invention.
Electrode assemblie with dividing plate and the secondary cell that comprises this electrode assemblie according to exemplary embodiment of the invention now will be described.
Shown in Fig. 2 A and 2B, dividing plate 20 according to the present invention comprises porous layer that is combined to form 60 and the polyolefin resin layer 70 by ceramic material and binding agent.By comparison diagram 2A and Fig. 2 B as can be known, the order of porous layer 60 and polyolefin layer 70 can be put upside down and not deviate from spirit of the present invention.More specifically, shown in Fig. 2 A and 2B, first electrode 16 comprises the active material layer 62 around collector 64.Equally, second electrode 18 also comprises the active material layer 66 around collector 68.Shown in Fig. 2 A, porous layer 60 can be positioned on the active material 62 of first electrode 16, and polyolefin resin layer 70 can be positioned on the porous layer 60, perhaps, shown in Fig. 2 B, polyolefin resin layer 70 can be positioned on the active material 62 of first electrode, and porous layer 60 is arranged on the polyolefin resin layer 70 then.
That is to say that according to the present invention, porous layer and polyolefin resin layer 70 all play the effect of dividing plate 20 in secondary cell.
At first, polyolefin resin layer 70 can comprise three layers of polyethylene (PE) individual layer, polypropylene (PP) individual layer or PP-PE-PP.But, the invention is not restricted to the polyolefin resin layer of mentioned kind and form.
Secondly, porous layer 60 can being combined to form by ceramic material and binding agent.
Ceramic material can comprise and being selected from by silicon dioxide (SiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2) and titanium oxide (TiO
2) at least a in the group that constitutes.Perhaps, ceramic material can comprise and is selected from a kind of in the group that is made of zirconium, aluminium, silicon and titanium insulative nitride, hydroxide, ketone and their mixture separately.Because be not suitable for according to ceramic material of the present invention such as titanium nitride conductive nitrides such as (TiN), so point out to be insulative nitride.
Binding agent can comprise the synthetic rubber latex binder or have the acrylic rubber binding agent of cross-linked structure.
Above-mentioned synthetic rubber latex binder can comprise at least a polymer emulsion that is selected from the group that is made of butadiene-styrene rubber (SBR) latex, acrylonitrile-butadiene rubber (NBR) latex, MMB methyl methacrylate butadiene rubber latex, chloroprene rubber latex, carboxylation styrene butadiene rubber latex and modified polyorganosiloxanes base polymer latex.These polymer emulsions can comprise water dispersant.Based on the electrode active material of 100 weight portions, the polymer emulsion solids content can be 0.1～20 weight portion.When use was lower than the polymer latex milk solids of 0.1 weight portion, porous layer can be not firm to adhering to of collector.When the polymer latex milk solids that uses greater than 20 weight portions, polymer emulsion can have a negative impact to battery behavior.
In addition, above-mentioned acrylic rubber binding agent with cross-linked structure can obtain by the cross-linking reaction of acrylic compounds main body polymer of monomers or copolymer and cross-linking comonomer.When only using acrylic compounds main body polymer of monomers or copolymer, the weak and disconnection easily of connected structure.But, when acrylic compounds main body monomer combines with cross-linking comonomer owing to cross-linking reaction, can form network structure more closely.Along with crosslinking degree increases, have cancellated polymer and in solvent, become and more be difficult to swelling.Based on the backbone molecule of 10,000 molecular weight unit, the acrylic rubber binding agent with cross-linked structure can have the 3 dimension cross-linked structures that comprise 2～10 crosslinking points, more specifically, comprises 4～5 crosslinking points.Thereby the acrylic rubber binding agent that has cross-linked structure according to the present invention can have good anti-swelling in electrolyte.
Above-mentioned ceramic material can decompose under about 1000 ℃ or higher temperature, and binding agent can be the acrylic rubber binding agent with cross-linked structure, and this binding agent can decompose under about 250 ℃ or higher temperature.Thereby the thermal endurance that can improve secondary cell is to improve the battery security for internal short-circuit.
Aforesaid propylene acids main body monomer can comprise select at least a from following group: a kind of alkoxyalkyl acrylate of selecting from the group that acrylic acid methoxyl group methyl esters, acrylic acid methoxyl group ethyl ester, acrylic acid ethoxy ethyl ester, acrylic acid butoxy ethyl ester, acrylic acid methoxy ethoxy ethyl ester and acrylic acid two cyclopentene oxygen base ethyl esters constitute; From metering system vinyl acetate, vinyl acrylate, allyl methacrylate, methacrylic acid-1,1-dimethyl allene ester, acrylic acid-1,1-dimethyl allene ester, methacrylic acid-3,3-neohexene ester and acrylic acid-3, a kind of acrylic acid alkenyl esters or the methacrylic acid alkenyl esters selected in the group that 3-neohexene ester constitutes; Be selected from a kind of unsaturated dicarboxylic ester of divinyl itaconate and divinyl maleate; Be selected from vinyl-1,1-dimethyl propylene thiazolinyl ether and vinyl-3, a kind of vinyl ethers of 3-dimethyl butyrate thiazolinyl ether; 1-acryloxy-1-styrene; And methyl methacrylate.
Above-mentioned crosslinked comonomer can comprise select at least a from following group: be selected from a kind of alkyl acrylate in the group that is made of 2-EHA, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate and Isooctyl acrylate monomer; Be selected from vinyl chloride for acetate and propenyl chloride a kind of thiazolinyl monochloroacetic acid ester for acetate; Be selected from a kind of ethylene oxidic ester or ether in the group that constitutes by glycidyl acrylate, vinyl glycidyl ether and acrylic glycidol ether; Be selected from a kind of unsaturated carboxylic acid in the group that constitutes by acrylic acid, methacrylic acid and maleic acid; 2-chloroethyl vinyl ethers; 1-chloro-4-methyl-benzene; And acrylonitrile.
Comprise that the dividing plate 20 by the porous layer that is combined to form 60 of ceramic material and binding agent and polyolefin resin layer 70 can have the thickness of about 16～22 μ m.
When dividing plate 20 has thickness less than 16 μ m, thereby be difficult to make anodal and negative pole is isolated mutually and is difficult to prevent short circuit.When dividing plate 20 has thickness greater than 22 μ m, have identical size in order to make secondary cell, reduced to have the thickness of structure of battery capacity.Thereby the battery capacity of secondary cell 10 can reduce.
In this case, the porous layer 60 that is equivalent to ceramic separator can have the thickness of about 4～6 μ m, and the polyolefin resin layer 70 that is equivalent to film type separator can have the thickness of about 12～16 μ m.
When porous layer 60 had thickness less than 4 μ m, the mechanical stability of secondary cell can reduce.By contrast, when porous layer 60 has thickness greater than 6 μ m, can improve mechanical stability.But because the thickness of polyolefin resin layer 70 reduces relatively, the heat of secondary cell exposes characteristic and can reduce.In addition, the porous layer 60 that ceramic material forms has the resistance higher than polyolefin resin layer 70, thereby has shortened the life-span of secondary cell.
When polyolefin resin layer 70 had thickness less than 12 μ m, heat exposed characteristic and can reduce.By contrast, when polyolefin resin layer 70 had thickness greater than 16 μ m, because the thickness of porous layer 60 reduces relatively, the mechanical stability of lithium rechargeable battery can variation, and resistive layer can thickening, thus the life-span of having reduced lithium rechargeable battery.
Therefore, porous layer 60 (being ceramic separator) can have the thickness of about 4～6 μ m, and polyolefin resin layer 70 (being film type separator) can have the thickness of about 12～16 μ m.
Secondly, the secondary cell 10 that comprises the electrode assemblie 14 of dividing plate 20 and comprise electrode assemblie 14 comprises anodal 18 and negative pole 16.
Anodal 18 can comprise the positive electrode active materials that can reversibly embed with the de-embedding lithium ion.The representative instance of positive electrode active materials can be such as LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2O
4And LiNi
1-x-yCo
xM
yO
2Lithium-transition metal oxides such as (0≤x≤1,0≤y≤1,0≤x+y≤1, M is Al, Sr, Mg or La metal).But, the invention is not restricted to the positive electrode active materials of mentioned kind.
In order to improve conductance, positive pole 18 and negative pole 16 can further comprise conductive agent separately.Conductive agent can comprise select at least a from the group that is made of graphite, carbon black, metal conductive agent and metallic compound conductive agent.For example graphite can be electrographite and native graphite.For example carbon black can be acetylene black, Ketjen black (ketjen black), Deng Kahei (denka black), thermal black and channel carbon black.For example metal or metallic compound conductive agent can be tin (Sn), tin oxide, phosphoric acid tin (SnPO
4), titanium oxide, potassium titanate and such as LaSrCoO
3And LaSrMnO
3Deng perovskite material.
The binding agent that is used for electrode active material can help to form the slurry of electrode active material, make electrode active material expansion and contraction bonding mutually, that electrode active material is adhered to collector and reduces electrode active material.For example, the binding agent that is used for electrode active material can comprise polyvinylidene fluoride, polyhexafluoropropylene-polyvinylidene fluoride copolymer (P (VdF/HFP)), polyvinyl acetate, polyvinyl alcohol, poly(ethylene oxide) (PEO), PVP, alkylation poly(ethylene oxide), polyvingl ether, polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyvinylpyridine, butadiene-styrene rubber and acrylonitrile-butadiene rubber.Based on the total weight of electrode active material, the consumption of binding agent is 0.1～30wt% (more specifically, 1～10wt%).When the binding agent consumption was lower than 0.1wt%, electrode active material was bonding not firm to collector.Equally, and when the binding agent consumption is higher than 30wt%, can guarantee electrode active material bonding firm to collector.Yet,, be difficult to increase the capacity of lithium rechargeable battery because the content of electrode active material reduces relatively.
The dispersion solvent that is used for dispersive electrode active material, binding agent and conductive agent can be nonaqueous solvents or aqueous solvent.Nonaqueous solvents can comprise N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide (DMF), dimethyl propylene acid amides (DMAC), N, N-dimethylaminopropylamine, oxirane or oxolane (THF).
When organic binding agent was used for porous layer, the solvent of porous slurry can pass through with 0: 100～50: 50, and for example 30: 70 weight ratio is mixed N-methyl pyrrolidone or NMP and cyclohexanone and obtained, and for example mixes with 30: 70 weight ratio.In the case, NMP can be replaced by isopropyl alcohol, toluene or dimethylbenzene.When the binding agent that forms negative active core-shell material was organic binder bond, the binding agent that forms the porous slurry can be an aqueous binders, and the solvent of porous slurry can be a water.
Equally, anodal 18 can comprise the plus plate current-collecting body that is formed by aluminium (Al) or Al alloy.Negative pole can comprise the negative current collector that is formed by copper (Cu) or Cu alloy.Plus plate current-collecting body and negative current collector can provide with the form of paper tinsel, film, sheet, perforation structure, loose structure or pumiceous texture separately.
As mentioned above, in the present invention, porous layer 60 and polyolefin resin layer 70 all can play dividing plate 20 in secondary cell 10.Equally, porous layer 60 and vistanex 70 can be formed on anodal 18 and negative pole 16 at least one on, and anodal and negative pole can pile up or both pile up and the formation electrode group of reeling.
In the case, after porous layer 60 was coated on anodal active material layer or the anode active material layer, polyolefin resin layer 70 can be arranged on the porous layer 60 in the mode shown in Fig. 2 B.Perhaps, after polyolefin resin layer 70 was arranged on anode active material layer or the anode active material layer, porous layer can be coated on the polyolefin resin layer 70.But, the invention is not restricted to the stacking order of above-mentioned porous layer and polyolefin resin layer.
The polyolefin resin layer that is equivalent to film type separator at high temperature shrinks, and the porous layer that is equivalent to ceramic separator at high temperature neither shrinks and also do not melt.If be the vistanex dividing plate, when internal short-circuit occurring, the part that the impaired part that causes with initial heating is adjacent is shunk always or is melted, and makes the combustion parts of film type separator enlarge, thereby causes more serious short circuit.On the contrary, form the positive pole of porous layer and/or negative pole on it only by the internal short-circuit slight damage, and impaired part can not enlarge.
Therefore, according to the present invention, the ceramic separator of porous layer can remedy fusing and the contraction under about 120 ℃ or higher temperature of film type separator that polyolefin resin layer forms.Particularly define the thickness of ceramic separator and film type separator, thereby make battery security maximization and do not reduce battery performance.
Secondly, comprise that the secondary cell of electrode assemblie comprises electrolyte, this electrode assemblie has according to dividing plate of the present invention.
According to the present invention, above-mentioned electrolyte can comprise non-aqueous organic solvent.This non-aqueous organic solvent can be carbonic ester, ester, ether or ketone.Carbonic ester can be dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid methyl propyl ester (MPC), carbonic acid ethyl propyl ester (EPC), carbonic acid methyl ethyl ester (MEC), ethylene carbonate (EC), propylene carbonate (PC) or butylene carbonate (BC).Ester can be butyrolactone (BL), decalactone, valerolactone, mevalonolactone, caprolactone, methyl acetate, ethyl acetate or n-propyl acetate.Ether can be dibutyl ethers, and ketone can be poly-methyl vinyl ketone.But the invention is not restricted to the non-aqueous organic solvent of mentioned kind.
When above-mentioned non-aqueous organic solvent was the carbonic ester organic solvent, the mixture of cyclic carbonate and linear carbonate can be used as non-aqueous organic solvent.In the case, for obtaining good electrolyte performance, cyclic carbonate and linear carbonate can be mixed with 1: 1～1: 9 volume ratio, more specifically, mix with 1: 1.5～1: 4 volume ratio.
Can obtain by in carbonate solvent, adding the aromatic hydrocarbon organic solvent according to electrolyte of the present invention.This aromatic hydrocarbon organic solvent can be a compound aromatic hydrocarbon.
For example, above-mentioned aromatic hydrocarbon organic solvent can be benzene, fluorobenzene, chlorobenzene, nitrobenzene, toluene, fluorotoluene, benzotrifluoride or dimethylbenzene.When electrolyte further comprised the aromatic hydrocarbon organic solvent, in order to obtain good electrolyte performance, carbonate solvent and aromatic hydrocarbon solvent can mix with 1: 1～30: 1 volume ratio.
In addition, can comprise as the lithium salts of lithium ion source according to electrolyte of the present invention to guarantee that lithium rechargeable battery operates substantially.For example, above-mentioned lithium salts can comprise and being selected from by LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, LiAlO
4, LiAlCl
4, LiN (C
XF
2X+1SO
2) (C
yF
2y+1SO
2) (x and y are natural numbers herein), LiSO
3CF
3And select in the group that constitutes of their mixture a kind of.
The working concentration of above-mentioned lithium salts is about 0.6～2.0M, more specifically, and 0.7～1.6M.When lithium salt was lower than 0.6M, electrolyte conductivity was low and can not present superperformance.When lithium salt is higher than 2.0M, the high and reduction lithium ion mobility of electrolyte viscosity.
According to the present invention, aforementioned barriers is inserted between positive pole and the negative pole, and anodal and negative pole piles up or both pile up and the formation electrode group of reeling.Thereafter, this electrode group is inserted in the jar or in the similar shell, then it is injected electrolyte, thereby finishes the manufacturing of lithium rechargeable battery.
Equally, can have cylindrical, square or bag shape according to the secondary cell of said method manufacturing, but be not limited thereto.
Below will illustrate according to an illustrative embodiment of the invention and Comparative Examples.But the present invention can multi-formly implement, and should not be construed as the illustrative embodiments that is subject in this statement.
Execution mode 1
Will be as the LiCoO of positive electrode active materials
2, mix with 92: 4: 4 weight ratio as the polyvinylidene fluoride (PVDF) of binding agent with as the carbon of conductive agent, and be dispersed in the N-N-methyl-2-2-pyrrolidone N-(NMP), thereby make anode sizing agent.This anode sizing agent is coated on the thick aluminium foil of 20 μ m the dry and formation positive pole of reeling.Will be as the Delanium of negative active core-shell material, mix with 96: 2: 2 weight ratio as the butadiene-styrene rubber of binding agent with as the carboxymethyl cellulose (CMC) of tackifier, and be dispersed in the water, thereby make cathode size.This cathode size is coated on the thick Copper Foil of 15 μ m the dry and formation negative pole of reeling.
Comprise by the porous layer that is combined to form of ceramic material and binding agent and the dividing plate of polyolefin resin layer and being inserted between positive pole and the negative pole.With anodal, negative pole and insert that dividing plate between them is reeled, compression and inserting in the cylindrical tank.
Form the thick porous layer of about 4 μ m, and form the thick polyolefin resin layer of about 12 μ m.
Electrolyte injected manufacturing that cylindrical tank finish lithium rechargeable battery thereafter.
Execution mode 2
Carry out the technology identical, distinguish and be to form the thick polyolefin resin layer of about 16 μ m with execution mode 1.
Execution mode 3
Carry out the technology identical, distinguish and be to form the thick porous layer of about 6 μ m with execution mode 1.
Execution mode 4
Carry out the technology identical, distinguish and be to form the thick porous layer of about 6 μ m, and form the thick polyolefin resin layer of about 16 μ m with execution mode 1.
Comparative Examples 1
Carry out the technology identical, distinguish and be to form the thick porous layer of about 2 μ m, and form the thick polyolefin resin layer of about 20 μ m with execution mode 1.
Comparative Examples 2
Carry out the technology identical, distinguish and be to form the thick polyolefin resin layer of about 10 μ m with execution mode 1.
Comparative Examples 3
Carry out the technology identical, distinguish and be to form the thick polyolefin resin layer of about 18 μ m with execution mode 1.
Comparative Examples 4
Carry out the technology identical, distinguish and be to form the thick porous layer of about 8 μ m, and form the thick polyolefin resin layer of about 10 μ m with execution mode 1.
Comparative Examples 5
Carry out the technology identical, distinguish and be to form the thick porous layer of about 6 μ m, and form the thick polyolefin resin layer of about 10 μ m with execution mode 1.
Comparative Examples 6
Carry out the technology identical, distinguish and be to form the thick porous layer of about 6 μ m, and form the thick polyolefin resin layer of about 18 μ m with execution mode 1.
To under constant current-constant voltage (CC-CV), charge to the charging voltage of ending of 4.2V according to each lithium rechargeable battery of execution mode 1～4 and Comparative Examples 1～6 manufacturing, and under CC, be discharged to the ending discharge voltage of 3V with the charge/discharge speed of 1C with the charge/discharge speed of 0.5C.Carry out charge-discharge cycles 100 times, and calculate the capability retention that obtains during the 100th charge-discharge cycles to measure the 100th time capacity to the percentage of capacity (%) first.
Equally, mensuration is according to the collision characteristic of each lithium rechargeable battery of execution mode 1～4 and Comparative Examples 1～6 manufacturing.This collision characteristic uses the standard charging lithium rechargeable battery to measure.Particularly, each lithium rechargeable battery level is placed on the black iron plate, the bar of 15.8mm diameter is placed on the lithium rechargeable battery, make axially vertical mutually.Afterwards, be that the counterweight of 9.1kg freely falls on the bar from the height of 610 ± 25mm with quality, make the collision of bar and lithium rechargeable battery.At this moment, with the bottom that thermel is linked lithium rechargeable battery, the battery surface variation of temperature after analyzing rod and the battery collision and the variation of battery.
For by crash tests, this lithium rechargeable battery must keep L1 level or even lower level other.Particularly, the L0 level is the state that no change takes place, the L1 level is the state that seepage takes place, the L2 level is that the battery surface temperature is lower than 200 ℃ and the state of smoldering, the L3 level is that the battery surface temperature is 200 ℃ or state higher and that smolder, the L4 level is the state that catches fire, and the L5 level is the state that explosion or blast occur.
After measuring the collision characteristic of each lithium rechargeable battery, when battery is L1 level or even lower level when other, the result is expressed as " qualified ", and when battery was L2 level or higher level, the result was expressed as " defective ".
In addition, mensuration exposes characteristic according to the heat of each lithium rechargeable battery of execution mode 1～4 and Comparative Examples 1～6 manufacturing.Particularly, the standard charging lithium rechargeable battery is packed in the chamber, be heated to about 130 ℃ temperature from normal temperature, under about 130 ℃ temperature, kept 1 hour, observe the variation of battery simultaneously with the programming rate of 5 ℃/min.In order to expose test by this heat, lithium rechargeable battery must keep L1 level or even lower level other when exceeding 10 minutes under about 130 ℃ temperature.
Particularly, the L0 level is the state that no external change takes place, and is the state that flash of light takes place and only observes ne-leakage, or the battery state that keeps sealing and be out of shape because of shock test.The L1 level is to have lost part battery accommodating thing (for example electrolyte) and make the battery initial weight reduce by 0.1% state at least, be owing to the shortcoming in the design make may be impaired part (for example outlet) impaired state takes place, or bore hole can be from visual observation to for example state of electrolytical injection sign.In order to confirm to leak, after carrying out corresponding test, must measure battery weight and compare with initial weight.But when security test, the process of mensuration and comparison battery weight can be omitted.In addition, the L1 level can be cell apparatus because of shock test impaired and electrolyte leakage takes place but not with smolder, the jet or state that catches fire.The L2 level is that the battery surface temperature is lower than about 200 ℃ and smolder but not with overheated state.For example, in the L2 level, by producing steam in the battery.The L3 level is to smolder and surpass 200 ℃ and the state that seriously steams with overheated, battery surface temperature, even or the outside vestige of not observing cigarette, but the surface temperature of battery is because of the overheated state that surpasses 200 ℃.The L4 level is that the battery accommodating thing spontaneously ignites, sends flame and lasting state with strong flame combustion, or supposes the state that ignites based on the burn pattern that battery case stays.The L5 level is that internal structure is discharged because of inner pressure of battery, and the part battery container, be not be because of the weakness in the design may be impaired be partially damaged, make the part exhaust of impaired housing.
After the heat of measuring each lithium rechargeable battery exposed characteristic, when battery is L1 level or even lower level when other, this result was expressed as " qualified ", and when battery was L2 level or higher level, this result was expressed as " defective ".Measurement result is listed in table 1.
Table 1
| Grouping | Porous layer thickness (μ m) | Vistanex layer thickness (μ m) | The 100th capacity is to the percentage of capacity (%) first | Collision characteristic | Heat exposes characteristic |
| Execution mode 1 | ??4 | ??12 | ??93 | Qualified | Qualified |
| Execution mode 2 | ??4 | ??16 | ??92 | Qualified | Qualified |
| Comparative Examples 1 | ??2 | ??20 | ??89 | Defective | Qualified |
| Comparative Examples 2 | ??4 | ??10 | ??94 | Qualified | Defective |
| Comparative Examples 3 | ??4 | ??18 | ??87 | Qualified | Qualified |
| Execution mode 3 | ??6 | ??12 | ??92 | Qualified | Qualified |
| Execution mode 4 | ??6 | ??16 | ??91 | Qualified | Qualified |
| Comparative Examples 4 | ??8 | ??10 | ??85 | Qualified | Defective |
| Comparative Examples 5 | ??6 | ??10 | ??93 | Qualified | Defective |
| Comparative Examples 6 | ??6 | ??18 | ??86 | Qualified | Qualified |
With reference to table 1, relatively execution mode 1 and Comparative Examples 1, although the gross thickness of porous layer and polyolefin resin layer is greater than the gross thickness of execution mode 1 in the Comparative Examples 1, the lithium rechargeable battery of making according to execution mode 1 obtains better result.Therefore as can be known, when porous layer thickness is 4 μ m or when bigger, good by the mechanical safety of collision characteristic reflection.
Relatively execution mode 1 and Comparative Examples 2 as can be known, when polyolefin resin layer too thin (10 μ m or lower), the heat of battery exposes characteristic and reduces.Polyolefin resin layer at high temperature melts and absorbs heat.And when polyolefin layer has 10 μ m or lower thickness, estimate that endothermic reaction meeting reduces, expose characteristic thereby reduce heat.
Relatively execution mode 2 and Comparative Examples 3, when polyolefin resin layer too thick (18 μ m or thicker), resistive layer thickens, thereby has shortened the life-span of lithium rechargeable battery.
Relatively execution mode 4 and Comparative Examples 4, although the gross thickness of porous layer in the execution mode 4 and polyolefin resin layer greater than Comparative Examples 4, the life-span of the lithium rechargeable battery in the Comparative Examples 4 is shorter than the life-span of execution mode 4.This may be because porous layer has higher resistance than polyolefin resin layer.
Relatively execution mode 3 and Comparative Examples 5 are the same when comparing with Comparative Examples 2 with execution mode 1, when the vistanex layer thickness is 10 μ m or when lower, the heat of battery exposes the characteristic reduction.Polyolefin resin layer at high temperature melts and absorbs heat.And when polyolefin resin layer has 10 μ m or lower thickness, estimate that endothermic reaction meeting reduces, expose characteristic thereby reduce heat.That is to say that even the porous bed thickness, what obtain comes to the same thing.
Relatively execution mode 4 and Comparative Examples 6, when polyolefin resin layer too thick (18 μ m or thicker), resistive layer thickens, thereby shortens the life-span of lithium rechargeable battery.
Thereby according to the present invention, the porous layer that is equivalent to ceramic separator can form the thickness of about 4～6 μ m, and the polyolefin resin layer that is equivalent to film type separator can form the thickness of about 12～16 μ m.The thickness of ceramic separator and film type separator is limited in the above-mentioned scope, thereby makes battery security maximization and do not reduce battery performance.
As mentioned above, can make the battery security maximization and not reduce battery performance according to electrode assemblie of the present invention and secondary cell with this electrode assemblie.
In addition, secondary cell according to the present invention has excellent capability retention, heat exposes characteristic and mechanical safety.
Although describe the present invention with reference to illustrative embodiments more of the present invention, but what it will be understood by those skilled in the art that is, can carry out various modifications and changes and not deviate from the spirit or scope of the present invention the present invention, the spirit or scope of the present invention be limited by claim and equivalent thereof.
Claims (22)
1, a kind of electrode assemblie that is used for battery, described assembly comprises:
First electrode;
Second electrode;
Dividing plate, comprise porous layer and polyolefin resin layer with ceramic composition, wherein said porous layer has the thickness of 4～6 μ m, and described polyolefin resin layer has the thickness of 12～16 μ m, and wherein said porous layer and described polyolefin resin layer insert between first electrode and second electrode.
2, the electrode assemblie that is used for battery as claimed in claim 1, wherein said first electrode comprises the negative pole with anode active material layer, and described second electrode comprises the positive pole with anode active material layer.
3, the electrode assemblie that is used for battery as claimed in claim 2, wherein said porous layer and described polyolefin resin layer are formed on one deck at least in described anode active material layer and the described anode active material layer.
4, the electrode assemblie that is used for battery as claimed in claim 3, wherein said porous layer is coated on described anode active material layer or the described anode active material layer, and described polyolefin resin layer is arranged on the described porous layer.
5, the electrode assemblie that is used for battery as claimed in claim 3, wherein said polyolefin resin layer is arranged on described anode active material layer or the described anode active material layer, and described porous layer is coated on the described polyolefin resin layer.
6, the electrode assemblie that is used for battery as claimed in claim 1, wherein said polyolefin resin layer is formed by the material that is selected from by in the group of polyethylene (PE) individual layer, polypropylene (PP) individual layer and three layers of formation of PP-PE-PP.
7, the electrode assemblie that is used for battery as claimed in claim 1, wherein said porous layer comprises ceramic composition and binding agent.
8, the electrode assemblie that is used for battery as claimed in claim 7, the ceramic composition of wherein said porous layer comprise and being selected from by silicon dioxide (SiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), titanium oxide (TiO
2), zirconium, aluminium, silicon and titanium insulative nitride, hydroxide, ketone separately, and at least a material in the group of their mixture formation.
9, the electrode assemblie that is used for battery as claimed in claim 8, wherein said binding agent comprise the synthetic rubber latex binder or have the acrylic rubber binding agent of cross-linked structure.
10, the electrode assemblie that is used for battery as claimed in claim 9, wherein said synthetic rubber latex binder comprise at least a polymer emulsion that is selected from the group that is made of butadiene-styrene rubber (SBR) latex, acrylonitrile-butadiene rubber (NBR) latex, MMB methyl methacrylate butadiene rubber latex, chloroprene rubber latex, carboxylation styrene butadiene rubber latex and modified polyorganosiloxanes base polymer latex.
11, the electrode assemblie that is used for battery as claimed in claim 9, wherein said acrylic rubber binding agent with cross-linked structure forms by the cross-linking reaction of acrylic compounds main body polymer of monomers or copolymer and cross-linking comonomer.
12, the electrode assemblie that is used for battery as claimed in claim 9, wherein said acrylic rubber binding agent with cross-linked structure comprise 3 dimension cross-linked structures with 2～10 crosslinking points.
13, the electrode assemblie that is used for battery as claimed in claim 9, wherein based on the backbone molecule of 10,000 molecular weight unit, described acrylic rubber binding agent has 4～5 crosslinking points.
14, the electrode assemblie that is used for battery as claimed in claim 11, wherein said acrylic compounds main body monomer comprises select at least a from following group: a kind of alkoxyalkyl acrylate of selecting from the group that acrylic acid methoxyl group methyl esters, acrylic acid methoxyl group ethyl ester, acrylic acid ethoxy ethyl ester, acrylic acid butoxy ethyl ester, acrylic acid methoxy ethoxy ethyl ester and acrylic acid two cyclopentene oxygen base ethyl esters constitute; From metering system vinyl acetate, vinyl acrylate, allyl methacrylate, methacrylic acid-1,1-dimethyl allene ester, acrylic acid-1,1-dimethyl allene ester, methacrylic acid-3,3-neohexene ester and acrylic acid-3, a kind of acrylic acid alkenyl esters or the methacrylic acid alkenyl esters selected in the group that 3-neohexene ester constitutes; Be selected from a kind of unsaturated dicarboxylic ester of divinyl itaconate and divinyl maleate; Be selected from vinyl-1,1-dimethyl propylene thiazolinyl ether and vinyl-3, a kind of vinyl ethers of 3-dimethyl butyrate thiazolinyl ether; 1-acryloxy-1-styrene; And methyl methacrylate.
15, the electrode assemblie that is used for battery as claimed in claim 11, wherein said cross-linking comonomer comprises select at least a from following group: be selected from a kind of alkyl acrylate in the group that is made of 2-EHA, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate and Isooctyl acrylate monomer; Be selected from vinyl chloride for acetate and propenyl chloride a kind of thiazolinyl monochloroacetic acid ester for acetate; Be selected from a kind of ethylene oxidic ester or ether in the group that constitutes by glycidyl acrylate, vinyl glycidyl ether and acrylic glycidol ether; Be selected from a kind of unsaturated carboxylic acid in the group that constitutes by acrylic acid, methacrylic acid and maleic acid; 2-chloroethyl vinyl ethers; 1-chloro-4-methyl-benzene; And acrylonitrile.
16, a kind of secondary cell comprises:
According to any described electrode assemblie in the claim 1～15; With
Electrolyte.
17, secondary cell as claimed in claim 16, wherein said electrolyte comprise at least a non-aqueous organic solvent that is selected from following group: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid methyl propyl ester (MPC), carbonic acid ethyl propyl ester (EPC), carbonic acid methyl ethyl ester (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), butyrolactone (BL), decalactone, valerolactone, mevalonolactone, caprolactone, methyl acetate, ethyl acetate or n-propyl acetate, dibutyl ethers and poly-methyl vinyl ketone.
18, secondary cell as claimed in claim 16, wherein said electrolyte comprises the organic solvent that makes to carbonic ester organic solvent adding aromatic hydrocarbon organic solvent, and described carbonic ester organic solvent mixes with 1: 1～30: 1 volume ratio with described aromatic hydrocarbon organic solvent.
19, secondary cell as claimed in claim 16, wherein said electrolyte comprises lithium salts.
20, secondary cell as claimed in claim 19, wherein said lithium salts comprise and being selected from by LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, LiAlO
4, LiAlCl
4, LiN (C
XF
2X+1SO
2) (C
yF
2y+1SO
2) (x and y are natural numbers herein), LiSO
3CF
3And a kind of in the group that constitutes of their mixture.
21, secondary cell as claimed in claim 20, the working concentration of wherein said lithium salts are 0.6～2.0M (mol).
22, secondary cell as claimed in claim 21, the working concentration of wherein said lithium salts are 0.7～1.6M (mol).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6129708P | 2008-06-13 | 2008-06-13 | |
| US61/061,297 | 2008-06-13 | ||
| US12/276,237 | 2008-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101604767A true CN101604767A (en) | 2009-12-16 |
Family
ID=41470382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101457545A Pending CN101604767A (en) | 2008-06-13 | 2009-06-05 | Electrode assemblie and comprise the secondary cell of this electrode assemblie |
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| Country | Link |
|---|---|
| CN (1) | CN101604767A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859753A (en) * | 2010-04-19 | 2013-01-02 | 孙春植 | Separator for battery |
| CN103988341A (en) * | 2011-12-14 | 2014-08-13 | 株式会社Lg化学 | Electrode for electrochemical device and electrochemical device comprising the same |
| CN104377328A (en) * | 2013-08-14 | 2015-02-25 | 三星Sdi株式会社 | Rechargeable lithium battery |
| CN105405670A (en) * | 2015-11-25 | 2016-03-16 | 山东精工电子科技有限公司 | Supercapacitor |
| CN106159163A (en) * | 2016-08-31 | 2016-11-23 | 合肥国轩高科动力能源有限公司 | A kind of power lithium-ion battery ceramic coating membrane and preparation method |
| CN108140876A (en) * | 2015-10-26 | 2018-06-08 | 株式会社日立制作所 | The manufacturing method of lithium rechargeable battery and lithium rechargeable battery |
| CN112567547A (en) * | 2018-04-27 | 2021-03-26 | 陶氏环球技术有限责任公司 | Solvent system for lithium ion battery pack production |
| CN113614959A (en) * | 2019-04-26 | 2021-11-05 | 陶氏环球技术有限责任公司 | Polyvinylpyrrolidone as a dispersant for the production of lithium ion battery cathodes |
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2009
- 2009-06-05 CN CNA2009101457545A patent/CN101604767A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859753A (en) * | 2010-04-19 | 2013-01-02 | 孙春植 | Separator for battery |
| CN102859753B (en) * | 2010-04-19 | 2015-07-29 | 孙春植 | Battery separators |
| US9515307B2 (en) | 2010-04-19 | 2016-12-06 | Chun Shig SOHN | Separator for battery |
| CN103988341A (en) * | 2011-12-14 | 2014-08-13 | 株式会社Lg化学 | Electrode for electrochemical device and electrochemical device comprising the same |
| CN104377328A (en) * | 2013-08-14 | 2015-02-25 | 三星Sdi株式会社 | Rechargeable lithium battery |
| CN108140876A (en) * | 2015-10-26 | 2018-06-08 | 株式会社日立制作所 | The manufacturing method of lithium rechargeable battery and lithium rechargeable battery |
| CN105405670A (en) * | 2015-11-25 | 2016-03-16 | 山东精工电子科技有限公司 | Supercapacitor |
| CN106159163A (en) * | 2016-08-31 | 2016-11-23 | 合肥国轩高科动力能源有限公司 | A kind of power lithium-ion battery ceramic coating membrane and preparation method |
| CN112567547A (en) * | 2018-04-27 | 2021-03-26 | 陶氏环球技术有限责任公司 | Solvent system for lithium ion battery pack production |
| CN113614959A (en) * | 2019-04-26 | 2021-11-05 | 陶氏环球技术有限责任公司 | Polyvinylpyrrolidone as a dispersant for the production of lithium ion battery cathodes |
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Open date: 20091216 |