CN103078076A - Composite diaphragm and lithium ion battery employing same - Google Patents
Composite diaphragm and lithium ion battery employing same Download PDFInfo
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- CN103078076A CN103078076A CN2013100104650A CN201310010465A CN103078076A CN 103078076 A CN103078076 A CN 103078076A CN 2013100104650 A CN2013100104650 A CN 2013100104650A CN 201310010465 A CN201310010465 A CN 201310010465A CN 103078076 A CN103078076 A CN 103078076A
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Abstract
The invention discloses a composite diaphragm and a lithium ion battery employing the same. The composite diaphragm adopts a three-layer structure, which comprises an organic substrate layer and two processing layers attached to the porous organic substrate, wherein a first processing layer attached to the substrate comprises an elastic polymer material and a binder; and a second processing layer attached to the first processing layer comprises nanoscale inorganic particles and a binder. The lithium ion battery employs the composite diaphragm. Compared with the prior art, the composite diaphragm is provided with a processing layer which adopts the high-elasticity material, therefore stress of electrodes of the lithium ion battery caused by volume change in charge-discharge processes can be buffered effectively, thereby effectively preventing battery pole pieces and the diaphragm from deformation in the charge-discharge processes; and simultaneously, the second processing layer provides high mechanical strength and thermal stability, so that the lithium ion battery employing the composite diaphragm is provided with better cycle performance and safety performance.
Description
Technical field
The invention belongs to the lithium ion battery field, especially a kind of composite isolated film and use the lithium ion battery of this barrier film.
Background technology
Lithium ion battery is a kind of chemical energy storage device with high voltage and high-energy-density, just has been subject to extensive concern and the exploitation of research institution and commercial undertaking since invention.Lithium ion battery can be applicable to the consumer-elcetronics devicess such as mobile phone, panel computer, MP3, notebook computer, also can be applicable to electric automobile, the fields such as distributed energy storage.Particularly in recent years along with the fast development of electric automobile and wind energy, solar energy industry, the demand of lithium ion battery is acutely increased.
The battery core of lithium ion battery is structurally general by positive plate, negative plate be interval in the barrier film that prevents short circuit between the positive/negative plate and consist of.The lithium ion battery of prior art particularly consumer electronics uses the barrier film of lithium ion battery to use polyolefin film, be generally polyethylene, polypropylene or the two is compound, wherein poly fusing point 130-140 ℃, polyacrylic fusing point 160-170 ℃, when battery because inside or external cause and temperature when raising, barrier film can shrink, therefore be easy to cause the direct contact of positive/negative plate and short circuit, the large tracts of land short circuit that melting causes positive/negative plate can occur in barrier film after battery temperature further raise, thereby caused battery explosion, the security incident such as on fire.For this type of safety problem, a solution of industry is the processing layer that is adhering to one deck and be comprised of inorganic particle and binding agent at the single or double of polyolefine isolating film, form composite isolated film, because the higher thermal stability of inorganic particle, the thermal contraction of composite isolated film reduces greatly, the inorganic active layer also has higher mechanical strength simultaneously, also can reduce Li dendrite in the battery or metal fragment, collector burr etc. to puncture barrier film and cause the probability of short circuit, therefore improve the security performance of battery.
But, the positive and negative pole material of lithium ion battery has different volumes under different embedding lithium states, thereby the thickness of pole piece can ceaselessly change in the charge and discharge process, makes from film and is subject to stress, and charge and discharge cycles repeatedly will cause the barrier film distortion, so that the interface variation of barrier film and both positive and negative polarity, the hydraulic performance decline that causes battery, the processing layer of inorganic particle does not have benefit for this clear condition, because the elasticity of inorganic particle own is very low, fragility is high, can't cushion stress.More serious situation, because the interface variation of barrier film and negative pole may cause forming Li dendrite in negative terminal surface, Li dendrite punctures barrier film, causes the internal short-circuit of battery, may cause that battery is on fire, blast, the formation security incident.
In the past, also occurred ceramic powders and the compound preparation barrier film of polyolefine isolating film, the composite isolated film of these existing ceramic powders and polyolefine isolating film all be simply with ceramic powder suspension in solvent and binding agent, have that barrier film and electrolyte wetting capacity are poor, security capabilities is poor and unstable properties.
Recently, the method for ceramic powders occurred again the grafting of benzene semi-annular jade pendant acid derivative is obtained, still, these methods obtain ceramic powder with existing benzene semi-annular jade pendant acid derivative grafting and make ceramic barrier film, and the ceramic layer bonding force is poor, has reduced the useful life of lithium battery; Internal resistance when benzene semi-annular jade pendant acid derivative easily increases the battery use reduces cycle-index, and the overall performance of lithium battery is descended.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of composite isolated film that is applied to lithium ion battery that adopts organic granular processing layer preparation is provided, this barrier film bonding force is good, elasticity strong, with electrolyte infiltrate good, to discharge and recharge repeatedly barrier film not yielding.
For the deficiency that solves the problems of the technologies described above, the invention provides a kind of composite isolated film that is applied to lithium ion battery.
We study discovery, can alleviate the distortion of barrier film at polyolefin-based and the elastomeric polymeric layer of the surface attachment one deck cellulose barrier film, therefore, the invention provides a kind of composite isolated film, a surface or two lip-deep two-layer processing layers that it comprises the porousness organic substrate and is attached to the porousness organic substrate, wherein the first processing layer is attached directly on the organic substrate, comprise elastomeric polymer beads and binding agent, the second processing layer is attached on the first processing layer, comprises nano inorganic particles and binding agent.
The porousness organic substrate that composite isolated film of the present invention uses is preferably and is polyethylene, polypropylene or cellulose barrier film, perhaps is polypropylene and polyethylene composite isolated film.
The high resiliency polymer beads selects not have special restriction, only need in lithium ion battery, get final product by electrochemical stability, especially, polymer beads preferably has good absorbent properties to the electrolyte of lithium ion battery, can guarantee so the quick conduction of lithium ion in barrier film, the electrical property that is conducive to battery, based on above-mentioned consideration, high resiliency particle of the present invention comprises one or more of unsaturated rubber, saturated rubber, thermoplastic elastomer (TPE), and wherein unsaturated rubber comprises one or more of following material:
Natural rubber Natural rubber (NR), isoprene rubber Synthetic polyisoprene (IR), polybutadiene rubber Polybutadiene (BR), butadiene-styrene rubber Styrene-butadiene Rubber (copolymer of polystyrene and polybutadiene, SBR), acrylonitrile-butadiene rubber Nitrile rubber (copolymer of polybutadiene and acrylonitrile, NBR), neoprene Chloroprene rubber (CR);
Saturated rubber comprises one or more of following material:
Butyl rubber Isobutylene Isoprene Rubber (IIR) or Butyl Rubber, halogenated butyl rubber Halogenated butyl rubbers (chlorinated scoline chloro isobutylene isoprene rubber:CIIR; Brombutyl bromo isobutylene isoprene rubber:BIIR), ethylene propylene monomer and ethylene propylene diene rubber EPM (ethylene propylene rubber, a copolymer of ethylene and propylene) and EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and a diene-component), epichlorohydrin rubber Epichlorohydrin rubber (ECO), lactoprene Polyacrylic rubber (ACM, ABR), silicon rubber Silicone rubber (SI, Q, MVQ), fluorosioloxane rubber Fluorosilicone Rubber (FVMQ), fluorubber Fluoroelastomers (FKM, and FEPM), chlorosulfonated polyethylene Chlorosulfonated polyethylene (CSM), (Hypalon), hydrogenated nitrile-butadiene rubber Hydrogenated Nitrile Rubbers (HNBR).
Thermoplastic elastomer (TPE) comprises one or more of following material:
Thermoplastic polyolefin elastomer Thermoplastic Elastomer-Olefine (TPE-O, TEO), thermoplastic styrene class elastomer Styrenic thermoplastic elastomer (TES, TPE-S), polyurethanes thermoplastic elastomer (TPE) Themoplastic Polyurethane elastomer (TPE-U, TPU), polyesters thermoplastic elastomer (TPE) Thermoplastic polyester elastomer (TPE-E, TEEE), thermoplastic polyamide elastomer Polyamide thermoplastic elastomer (TPE-A), halogen-containing thermoplastic elastomer Thermoplastic Halogenated elastomer, ionic thermoplastic elastomer (TPE) Ionic thermoplastic elastomer, ethylene copolymer thermoplastic elastomer (TPE) Ethylene copolymer thermoplastic elastomer (EVA), 1,2-polybutadiene thermoplastic elastomer (TPE) Thermplastic 1,2-poly-butadiene elastomer, using trans-polyisoprene thermoplastic elastomer (TPE) Thermoplastictrans-polyisoprene elastomer, melt processible thermoplastic elastomer (TPE) Melt Processible thermoplastic elastomer (trade name Alcryn), thermoplastic sulfurized rubber Themoplastic Vulcanizates (TPV).
Inorganic particle in the second processing layer of the present invention selects not have particular restriction, only need to be in lithium ion battery electrochemical stability, but the higher material with self having the lithium ion Effective Conductivity of preferred dielectric constant, this is because high dielectric constant can promote electrolyte in the lithium ion battery from solution, electrolytic conductivity is provided, and the lithium-ion electric of inorganic particle self is led ability, and also the electrical property to battery is useful.Based on above-mentioned consideration, inorganic particle of the present invention is preferably: SiO
2, Al
2O
3, CaO, TiO
2, ZnO, MgO, ZrO
2, SnO
2, BaSO
4, AlPO
4, AlF
3, ZnF
2, ZrF
4, LiF, BaTiO
3In any one or a few.
The pore size of described the first and second processing layers and porosity depend primarily on the particle diameter of polymer beads and inorganic particle, and when using particle diameter to be 1 μ m or lower particle, the hole of formation has 1 μ m or lower aperture.Above-mentioned pore structure can be full of the electrolyte of injection subsequently, and used for electrolyte is in the conduction inorganic ions, and therefore, pore size and porosity are the important tired elements of the ionic conductivity of control composite isolated film.The pore size of composite isolated film of the present invention is preferably 0.01-2 μ m, and porosity is preferably 5-75%, and therefore, polymer beads and inorganic particle size all are preferably the 50-2000 nanometer.
Described bonding agent is coupling agent, or polyacrylic acid, or the mixture of polyacrylic acid and polyacrylate, or coupling agent and polyacrylic mixture, or the mixture of coupling agent and polyacrylic acid, polyacrylate.
Composite isolated film of the present invention does not have particular restriction to thickness, and principle is for guaranteeing mechanical strength and the battery performance of barrier film, and the preferred thickness of film is 1-100 μ m, and optimum thickness is 2-30 μ m.
Composite isolated film of the present invention does not have particular restriction to the mixing ratio of inorganic particle, polymer beads and adhesive, can be according to the two rational proportion of the processing layer thickness that finally will form and structure control.
The general principles of the first processing layer practical function in the composite isolated film of the present invention is: in the battery charging process; cathode pole piece expands; barrier film is produced pressure; polymer composition granule in the first processing layer produces elastic deformation owing to having high elasticity, has absorbed the stress that pole piece expands and produces; organic substrate is formed cushioning effect; when battery discharge, stress is eliminated, and polymer beads is replied original state.If there is not polymer beads to exist, organic substrate experiences repeatedly the phenomenon that charge and discharge cycles can produce the distortion of crumpling so, causes that battery performance descends and potential safety hazard.The inorganic particle of the present invention's the second processing layer has high mechanical strength and thermal stability, thereby has guaranteed the intensity of whole composite isolated film and thermally-stabilised.The acting in conjunction of two kinds of processing layers is so that adopt the lithium ion battery of composite isolated film of the present invention to have better cycle performance and security performance.
Above-mentioned composite isolated film can adopt all existing making batteries technique of organic/inorganic porous compound film, namely be first the mixture of polymer beads and adhesive to be coated on the porous substrate, after the drying, form the first processing layer, and then the mixture of inorganic particle and adhesive is coated to formation the second processing layer on the first processing layer.
To achieve these goals, the present invention also provides a kind of lithium ion battery, and it comprises positive pole, negative pole, electrolyte and the interval barrier film between positive pole and negative pole, and wherein barrier film adopts the composite isolated film described in the above-mentioned paragraph.
As a kind of improvement of lithium ion battery, above-mentioned composite isolated film and micropore barrier film can also be used micropore barrier film such as polyolefin-based barrier film together as barrier film.
Lithium ion battery of the present invention can be made by conventional method well known by persons skilled in the art, in the embodiment of the method for making electrochemical appliance, composite isolated film is inserted in the basic battery structure of being assembled into of positive plate and negative plate, then injects electrolyte.
The present invention can apply electrode active material at current collector by method known to those skilled in the art and form the electrode slice that can use with composite isolated film of the present invention.Especially, positive electrode active materials can comprise the conventional positive electrode active materials that uses at present in the positive pole of electrochemical appliance, comprises LiCoO
2, LiMn
2O
4, LiNi
xCo
yMn
1-x-yO
2(0＜x＜1,0＜y＜1), LiFePO
4In one or more.Negative active core-shell material can comprise any conventional negative active core-shell material that uses at present in the negative pole of conventional lithium ion battery, comprises lithium metal, lithium alloy, carbon, petroleum coke, active carbon, graphite, Si or Li
4Ti
5O
12Cathode current collector comprises that by aluminium, nickel or its paper tinsel that is combined to form, the cathodal current current-collector comprises the paper tinsel that is formed by copper, gold, nickel, copper alloy or several alloys wherein.
The electrolyte that can use in electrochemical appliance of the present invention is by lithium salts and solvent composition.Can be used for lithium salts of the present invention comprises: LiPF
6, LiBF
4, LiClO
4, LiASF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2, dioxalic acid lithium borate (LiBOB), LiC (CF
2SO
2)
3In one or more.Optional solvent comprises: one or more in propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC) dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide (DMSO), acetonitrile, dimethoxy-ethane, oxolane, methyl formate (MF), methyl acetate (MA) and ethyl propionate (EP), methyl ethyl carbonate (EMC), the gamma-butyrolacton (GBL).But the electrolyte that uses in the present invention is not limited to above-mentioned example.
This composite isolated film lithium ion battery is difficult for the lithium ion battery of short circuit, safety, and this lithium ion battery internal resistance is difficult for increasing long service life, stable performance.
Description of drawings
Below in conjunction with the drawings and specific embodiments, to composite isolated film of the present invention, use the lithium ion battery of this barrier film and useful technique effect thereof to be elaborated.
Fig. 1 is the structural representation of composite isolated film of the present invention.
Fig. 2 be the 1C charging in the time of 60 ℃ of lithium ion battery IV, lithium ion battery II, lithium ion battery V ,-1C discharge cycles process in the graph of a relation of capability retention and cycle-index.
Fig. 3 be the 3C charging in the time of 60 ℃ of lithium ion battery IV, lithium ion battery II, lithium ion battery V ,-3C discharge cycles process in the graph of a relation of capability retention and cycle-index.
Fig. 4 is the discharge-rate Character Comparison figure of lithium ion battery IV, lithium ion battery II, lithium ion battery V.
Internal resistance comparison diagram when Fig. 5 is lithium ion battery IV, lithium ion battery II, the large multiplying power pulse direct current discharge of lithium ion battery V.
Embodiment
To composite isolated film of the present invention and use the lithium ion battery of this barrier film to be described in further detail, but embodiments of the present invention are not limited to this below with reference to specific embodiment.
1-1. composite isolated film (SBR particle, BaSO
4Particle) preparation:
Step (1): SBR powder (the D50=1.5 μ m that adds 50wt% (solids content metering) in the deionized water, high resiliency polymer beads of the present invention has caking property and can replace bonding agent to use, also can use binding agent well known in the art, lower same) stirring 1h, make slurry, then the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated on the polyethylene porous membrane that thickness is 16 μ m (porosity 45%), through oven drying, make the first processing layer of single face, repeat this step and obtain thick another side the first processing layer of 2 μ m.
Step (2): the BaSO that adds 50wt% in the deionized water
4Powder (D50=1.5 μ m) stirs 1h, then after the poly acrylic acid-poly PAA aqueous solution (content of poly acrylic acid-poly PAA in the aqueous solution is 25wt%) that adds solids content and be 5wt% stirs 1h, in grinding in ball grinder 1h, add again 5wt% in the slurry after the grinding, solids content is the CMC solution of 0.5wt%, continue to stir 1h, make slurry.Then on the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated in that step (1) obtains the two-sided composite isolated film that all has the first processing layer, obtain the second processing layer of single face through oven drying, thickness is 2 μ m, same method obtains thick another side the second processing layer of 2 μ m, and namely the gross thickness of composite isolated film is 24 μ m.With the composite isolated film that the mercury injection apparatus measurement makes, its porosity is 40%.
1-2. the manufacturing of lithium ion battery:
Anodal manufacturing: to the LiNi as positive electrode as adding 94wt% in the METHYLPYRROLIDONE (NMP) of solvent
0.333Co
0.333Mn
0.3333O
2, 2.0wt% as the carbon black of conductive agent and the PVDF(polyvinylidene fluoride as binding agent of 4.0wt%), make anode sizing agent.Anode sizing agent is coated on the Al paper tinsel as plus plate current-collecting body that thickness is 16 μ m, and drying obtains positive plate, then positive plate is carried out roll extrusion.
The manufacturing of negative pole: to as the powdered graphite as negative electrode active material that adds 94.5wt% in the deionized water of solvent, the carbon black as conductive agent of 2.0wt%, the CMC(sodium carboxymethylcellulose as thickener of 1.5wt%) and the SBR(butadiene-styrene rubber as binding agent of 2.0wt%), mix the formation cathode size.Cathode size is coated on the Cu paper tinsel as negative current collector that thickness is 9 μ m, and the dry negative plate that forms.Then the anticathode sheet carries out roll extrusion.
The manufacturing of battery: composite isolated film, positive plate and negative plate that above-mentioned steps makes are reeled together, make battery core; Then in battery core, inject electrolyte (solvent: ethyl acetate EC and methyl ethyl carbonate EMC, lithium salts: the LiPF of 1M concentration
6), obtain the lithium ion battery I after the encapsulation.
Method according to the present embodiment prepares positive plate, negative plate, and uses conventional polythene PE barrier film to make the lithium ion battery II.Barrier film has approximately 45% porosity.
The composite isolated film that use the present embodiment obtains is as sample, and use PE barrier film in contrast.Check the percent thermal shrinkage of each test piece after depositing 5 minutes under 200 ℃ the high temperature, the result shows: the shrinkage crimping owing to high temperature of PE barrier film, and become transparent; By contrast, the composite isolated film thermal contraction of the present embodiment is very little.As seen, composite isolated film of the present invention has good thermal stability.
2-1. composite isolated film (fluorubber particle, Al
2O
3Particle) preparation:
Step (1): in deionized water, add fluorubber powder (D50=2 μ m) the stirring 1h that quantity is about 50wt% (solids content metering), make slurry, polypropylene microporous film is improved film surface tension force through corona treatment in advance, then the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated on the polypropylene porous membrane that thickness is 20 μ m (porosity 48%), through oven drying, make the first processing layer of single face, thickness is 4 μ m, repeats this step and obtains thick another side the first processing layer of thickness 4 μ m.
Step (2): in deionized water, add the Al that quantity is about 50wt% (solids content metering)
2O
3Powder (D50=1 μ m) stirs 1h, then add the 20wt% solids content and be the PAA-PAAS aqueous solution of 5wt% and aqueous silane coupling agent (3-glycidol ether propyl-triethoxysilicane) that the 15wt% solids content is 3wt%, and after stirring 1h, in grinding in ball grinder 1h, adding solids content in the slurry after the grinding is the CMC solution of 1.0wt% again, continue to stir 1h, make slurry.Then on the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated in that step (1) obtains the two-sided composite isolated film that all has the first processing layer, obtain the second processing layer of single face through oven drying, thickness is 2 μ m, repeat this step and obtain the thick another side processing layer of thickness 2 μ m, namely the gross thickness of composite isolated film is 32 μ m.The porosity of the composite isolated film that makes with the mercury injection apparatus measurement is about 43%.
2-2. the manufacturing of lithium ion battery: step is identical with embodiment 1, and difference only is the composite isolated film that adopts the present embodiment to make to make the lithium ion battery III.
3-1. composite isolated film (TPE particle, Al
2O
3Particle) preparation:
Step (1) adds TPE powder (D50=1.5 μ m) the stirring 1h that quantity is about 50wt% (solids content metering) in deionized water, make slurry, the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated on the polyethylene porous membrane that thickness is 16 μ m (porosity 45%), through oven drying, make the first processing layer of single face, thickness is 2 μ m, repeats this step and obtains thick another side the first processing layer of thickness 2 μ m.
Step (2) adds the Al that quantity is about 50wt% (solids content metering) in deionized water
2O
3Powder (D50=1.3 μ m) stirs 1h, then add the PAA-PAAS aqueous solution of 20wt% take solid content meter content as 5wt% and the silane coupler (3-glycidol ether propyl trimethoxy silicane) 40% take solid content meter content as 3wt%, and after stirring 1h, in grinding in ball grinder 1h, adding solids content in the slurry after the grinding is the CMC solution of 0.5wt% again, continue to stir 1h, make slurry.Then on the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated in that step (1) obtains the two-sided composite isolated film that all has the first processing layer, obtain the second processing layer of single face through oven drying, thickness is 2 μ m, repeat this step and obtain the thick another side processing layer of thickness 2 μ m, namely the gross thickness of composite isolated film is 24 μ m.The porosity of measuring composite isolated film with mercury injection apparatus is about 41%.
3-2. the manufacturing step of lithium ion battery is identical with embodiment 1, difference only is the composite isolated film that adopts the present embodiment to make to make the lithium ion battery IV.
Method according to embodiment 1 prepares positive plate, negative plate, makes composite isolated film according to the method for the present embodiment, but only makes the second processing layer, namely directly with Al
2O
3The inorganic particle slurry is coated on the polyethylene barrier film, makes at last the lithium ion battery V.
4-1. composite isolated film (SBR/TPE hybrid particles, Al
2O
3Particle) preparation:
Step (1) adds TPE powder (D50=1.5 μ m) and 20wt%TPE powder (D50=1.5 μ m) the stirring 1h that quantity is about 30wt% (solids content metering) in deionized water, make slurry, the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated on the cellulose porous film (porosity 65%) that thickness is 20 μ m, through oven drying, make the first processing layer of single face, thickness is 2 μ m, repeats this step and obtains thick another side the first processing layer of thickness 2 μ m.
It is the Al of 15wt% (solids content metering) that step (2) adds quantity in the deionized water
2O
3Powder stirs 1h, then adds the PAA-PAAS aqueous solution take solid content meter content as 5wt %, and after stirring 1h, in grinding in ball grinder 1h, add again the CMC solution take solids content and content as 0.5wt% in the slurry after the grinding, continue to stir 1h, make slurry.Then on the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated in that step (1) obtains the two-sided composite isolated film that all has the first processing layer, obtain the second processing layer of single face through oven drying, thickness is 2 μ m, repeat this step and obtain the thick another side processing layer of thickness 2 μ m, namely the gross thickness of composite isolated film is 28 μ m.The porosity of measuring composite isolated film with mercury injection apparatus is 59%.
4-2. the manufacturing step of lithium ion battery is identical with embodiment 1, difference only is the composite isolated film that adopts the present embodiment to make to make the lithium ion battery VI.
The lithium battery safety evaluation
Drift bolt test: lithium ion battery I and VI sample and lithium ion battery II sample completely are charged to respectively 4.2V, and after leaving standstill 1 hour, measuring voltage and resistance penetrate each battery sample with the steel nail of diameter 3mm, while monitoring battery surface temperature, the situation of observing each battery sample.The result shows, lithium battery I and VI are not smoldered and not on firely do not exploded, and lithium ion battery II occurs obviously smoldering on fire.Therefore, use the lithium ion battery of composite isolated film of the present invention to have good puncture-resistant security performance.
Overcharge test: lithium ion battery I and VI sample and lithium ion battery II sample are discharged to respectively 2.8V, the electric current that re-uses 3C overcharge 10V to and kept the situation of observing each battery sample 2 hours.The result shows, lithium ion battery I and VI sample do not smolder, not on fire, do not explode, smoldering namely appears in 10V, phenomenon on fire and lithium ion battery II does not also arrive.Test result shows, adopts the lithium ion battery of composite isolated film of the present invention to have good overcharging resisting security performance.
Hot case test: lithium ion battery I and VI sample and lithium ion battery II sample completely are charged to respectively 4.2V and left standstill 1 hour, each battery sample is placed 150 ℃ of hot case half an hour, then check battery.Check result shows, lithium ion battery I and VI do not smolder, not on fire, do not explode; And lithium ion battery II all smolders, and is on fire.Therefore, adopt the lithium battery of composite isolated film of the present invention to show heat temperature resistant safe.
Squeeze test: lithium ion battery I and VI sample and lithium ion battery II sample completely are charged to 4.2V, between two arcs, push, until pressure reaches release pressure behind the 13KN, observe battery status.The result shows, lithium ion battery I and VI sample do not smolder, not on fire, also do not explode; And that lithium ion battery II sample is all smoldered is on fire.Illustrate and adopt the lithium battery of composite isolated film of the present invention to show good anti-extruding fail safe.
The cycle performance assessment of lithium ion battery
The 1C/1C charge and discharge cycles: employed sample is according to the lithium ion battery IV in this experiment, and uses lithium ion battery II and V in contrast.Shown in Figure 2 is that lithium ion battery IV, lithium ion battery II and V are carried out 1C charging and 1C discharge in the time of 60 ℃, the relation of capability retention and cycle-index, as we can see from the figure, lithium ion battery IV cycle performance of the present invention obviously is better than lithium ion battery II and V.
The 3C/3C charge and discharge cycles: employed sample is according to the lithium ion battery IV in this experiment, and uses lithium ion battery II and V in contrast.Shown in Figure 3 is that lithium ion battery IV, lithium ion battery II and V are carried out 3C charging and 3C discharge in the time of 60 ℃, the relation of capability retention and cycle-index, as we can see from the figure, the cycle performance of lithium ion battery of lithium ion battery IV of the present invention obviously is better than lithium ion battery II and V, and, compare and can find with the result of 1C/1C charge and discharge cycles experiment, do the circulation time of larger multiplying power when battery, composite isolated film of the present invention is more obvious to the improvement of cycle performance of battery.
The high rate performance evaluation of lithium ion battery
This experiment uses the lithium ion battery IV as sample, and uses lithium ion battery II and V in contrast.As shown in Figure 4, adopt the high rate performance of lithium ion battery of composite isolated film of the present invention and lithium ion battery II and V almost as broad as long, illustrate that the processing layer that increases one deck high resiliency polymer in composite isolated film can not affect the high rate performance of battery.
The DC internal resistance evaluation of lithium ion battery
The sample of this experiment is ion battery IV, lithium ion battery II and V, and the purpose of this experiment is to estimate the internal resistance of battery when large multiplying power pulse direct current discharge, the namely power-performance of characterizing battery.As shown in Figure 5, the internal resistance of ion battery IV and lithium ion battery II and V are almost as broad as long, illustrate that the processing layer that increases one deck high resiliency polymer in composite isolated film can not affect the power-performance of battery.
Book is described according to the above description, and those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not consist of any restriction to the present invention just for convenience of description.
Claims (10)
1. composite isolated film, it is characterized in that: comprise porousness organic substrate and the two-layer processing layer that is attached on the porousness organic substrate, the first processing layer that is attached on the base material comprises having elastomeric polymer beads and binding agent, and the second processing layer that is attached on the first processing layer comprises nano inorganic particles and binding agent.
2. composite isolated film according to claim 1 is characterized in that: have elastomeric polymer beads and be in the following material one or more: unsaturated rubber, saturated rubber, thermoplastic elastomer (TPE).
3. composite isolated film according to claim 2, it is characterized in that: unsaturated rubber is one or more in the following material: natural rubber, isoprene rubber, polybutadiene rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber, neoprene.
4. composite isolated film according to claim 2, it is characterized in that: saturated rubber is one or more in the following material: butyl rubber, halogenated butyl rubber, ethylene propylene monomer, ethylene propylene diene rubber, epichlorohydrin rubber, lactoprene, silicon rubber, fluorosioloxane rubber, fluorubber, chlorosulfonated polyethylene, hydrogenated nitrile-butadiene rubber.
5. composite isolated film according to claim 2, it is characterized in that: saturated rubber is one or more in the following material: thermoplastic polyolefin elastomer, thermoplastic styrene class elastomer, polyurethanes thermoplastic elastomer (TPE), polyesters thermoplastic elastomer (TPE), thermoplastic polyamide elastomer, halogen-containing thermoplastic elastomer, ionic thermoplastic elastomer (TPE), ethylene copolymer thermoplastic elastomer (TPE), 1,2-polybutadiene thermoplastic elastomer (TPE), using trans-polyisoprene thermoplastic elastomer (TPE), melt processible thermoplastic elastomer (TPE), thermoplastic sulfurized rubber.
6. composite isolated film according to claim 1, it is characterized in that: porous substrate is polyolefine thin film or cellophane.
7. composite isolated film according to claim 1, it is characterized in that: thickness is 1-100 μ m, and porosity is 5-75%.
8. composite isolated film according to claim 1, it is characterized in that: nano inorganic particles is one or more in the following material: SiO
2, Al
2O
3, CaO, TiO
2, ZnO, MgO, ZrO
2, SnO
2, BaSO
4, AlPO
4, AlF
3, ZnF
2, ZrF
4, LiF, BaTiO
3
9. composite isolated film according to claim 1, it is characterized in that: the particle diameter of nano inorganic particles is preferably the 50-2000 nanometer.
10. lithium ion battery, it comprises positive pole, negative pole, electrolyte and the interval barrier film between positive pole and negative pole, it is characterized in that: described barrier film adopts each described composite isolated film among the claim 1-9, and described barrier film also comprises polyolefin-based barrier film and the cellulose barrier film that uses with composite isolated film.
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| CN104377328A (en) * | 2013-08-14 | 2015-02-25 | 三星Sdi株式会社 | Rechargeable lithium battery |
| CN105440770A (en) * | 2014-06-30 | 2016-03-30 | 成都中科来方能源科技有限公司 | Water based composition used for modifying diaphragm for lithium ion battery and modified diaphragm and battery |
| CN105895844A (en) * | 2016-04-15 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Sticky ceramic diaphragm and preparation method thereof |
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| CN105440770A (en) * | 2014-06-30 | 2016-03-30 | 成都中科来方能源科技有限公司 | Water based composition used for modifying diaphragm for lithium ion battery and modified diaphragm and battery |
| CN105895844A (en) * | 2016-04-15 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Sticky ceramic diaphragm and preparation method thereof |
| CN110710023B (en) * | 2017-04-10 | 2023-11-03 | 纳米技术仪器公司 | Lithium metal secondary battery comprising anode-protecting polymer layer and method for manufacturing same |
| CN110710023A (en) * | 2017-04-10 | 2020-01-17 | 纳米技术仪器公司 | Lithium metal secondary battery containing polymer layer for protecting anode and manufacturing method thereof |
| US11264677B2 (en) | 2018-06-06 | 2022-03-01 | Ningde Amperex Technology Limited | Separator and electrochemical device |
| CN108899460B (en) * | 2018-07-10 | 2021-06-01 | 福建师范大学 | Preparation method of coating polymer film doped with aluminum phosphate coating agent |
| CN108899460A (en) * | 2018-07-10 | 2018-11-27 | 福建师范大学 | A kind of coated polymer membrane preparation method mixing phosphalugel coating agent |
| US11258137B2 (en) | 2018-12-28 | 2022-02-22 | Industrial Technology Research Institute | Aluminum-ion battery |
| CN113067095A (en) * | 2019-12-14 | 2021-07-02 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic diaphragm and preparation and application thereof |
| CN113067095B (en) * | 2019-12-14 | 2022-05-10 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic diaphragm and preparation and application thereof |
| CN110957456A (en) * | 2019-12-16 | 2020-04-03 | 国联汽车动力电池研究院有限责任公司 | Metal-free current collector composite electrode, preparation method thereof and lithium ion battery |
| CN113078414A (en) * | 2019-12-17 | 2021-07-06 | 山东海科创新研究院有限公司 | Polypropylene composite diaphragm with low-temperature thermal closed-cell mechanism, preparation method thereof and lithium ion battery |
| CN113745755A (en) * | 2021-08-23 | 2021-12-03 | 河北金力新能源科技股份有限公司 | Heat-resistant lithium battery diaphragm and preparation method thereof |
| CN114243203A (en) * | 2021-12-01 | 2022-03-25 | 远景动力技术(江苏)有限公司 | High-elongation diaphragm, preparation method thereof and lithium ion battery |
| CN114784441A (en) * | 2022-06-22 | 2022-07-22 | 宁德时代新能源科技股份有限公司 | Battery and power consumption device |
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