CN102969473A - Organic/inorganic composite porous thin film and electrochemical energy storing device using same - Google Patents
Organic/inorganic composite porous thin film and electrochemical energy storing device using same Download PDFInfo
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Abstract
The invention discloses an organic/inorganic composite porous thin film and an electrochemical energy storing device using the same. The organic/inorganic composite porous thin film comprises a porous organic base material and an active layer attached on the porous organic base material, wherein the active layer comprises inorganic particles and a binder, and the inorganic particles are one or mixture of sulfate, phosphate, metal fluoride and lithium salt. The organic/inorganic composite porous thin film is adopted as an isolating film for the electrochemical energy storing device. Compared with the prior art, the organic/inorganic composite porous thin film takes substances which do not react with hydrofluoric acid as the inorganic particles of the active layer, and therefore, the electrochemical energy storing device adopting the organic/inorganic composite porous thin film has the advantages of good circulating storage performance, high voltage resistance performance and safety performance.
Description
Technical field
The invention belongs to the electrochemical energy storage field, especially a kind of organic/inorganic composite porous film and use the electrochemical energy storage device of this film.
Background technology
In recent years, the quick of the portable electric appts such as mobile phone, notebook computer, panel computer popularized, the development of ev industry, wind energy and solar energy industry, and all to energy storage device, especially the demand of secondary cell increases day by day.Wherein, lithium ion battery has become the focus of research and business development owing to have higher driving voltage and energy density.
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.Traditional lithium ion battery barrier film is generally polyolefin film, its fusing point is lower, usually at 120-140 ℃ and 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 short circuit of positive/negative plate, 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.
Be to solve the problems referred to above that polyolefine isolating film brings, a solution of industry is that the single or double at polyolefin film adheres to the porous active layer that is comprised of inorganic particle and binding agent, the formation organic/inorganic composite film.Because the inorganic active layer has higher thermal stability, therefore the thermal contraction of whole laminated film is suppressed greatly, the inorganic active layer also has higher mechanical strength simultaneously, this can reduce also that Li dendrite in the battery or metal fragment, collector burr etc. puncture barrier film and the probability that causes short circuit, thereby has improved the security performance of battery.In addition, the inorganic active layer also has good electrolyte wettability, and is also helpful to the chemical property that improves battery.To adopt Al in the present inorganic active layer
2O
3, CaO, TiO
2, ZnO, MgO, ZrO
2, SnO
2, SiO
2Use as inorganic particle Deng oxide, still, because the lithium salts in the electrolyte of lithium ion battery is mainly LiPF
6, inevitably have a certain amount of water, LiPF in the electrolyte simultaneously
6Can generate hydrofluoric acid (HF) with the water reaction, hydrofluoric acid further reacts fluoride and the water that generates with inorganic particle, take inorganic particle as Al
2O
3The time be example, following chemical reaction: LiPF will occur in the battery
6→ LiF+PF
5PF
5+ H
2O → POF
3+ 2HF; 6HF+AL
2O
3→ 2ALF
3+ 3H
2O.As seen, water is not consumed in the above-mentioned series reaction, therefore reaction can continue to carry out, again because barrier film is that long period of soaking is in electrolyte, after reacting for a long time, different on the lattice volume of the fluoride that generates and reactant oxide will cause inorganic active layer generation change in volume, thereby active layer is come off from perforated substrate, and electrical property decay and the fail safe of battery descend.
In view of this, the necessary electrochemical energy storage device that a kind of more stable organic/inorganic composite porous film is provided and uses this film.
Summary of the invention
The object of the invention is to: a kind of more stable organic/inorganic composite porous film is provided and uses the electrochemical energy storage device of this film, to guarantee the long-time stability of barrier film in electrochemical energy storage device.
In order to realize the foregoing invention purpose, the inventor is through concentrating on studies, a kind of organic/inorganic composite porous film is provided, it comprises porousness organic substrate and the active layer that is attached on the porousness organic substrate, active layer comprises inorganic particle and binding agent, and inorganic particle is a kind of or several mixture in sulfate, phosphate, metal fluoride, the lithium salts.
Organic/inorganic composite porous film of the present invention acting as in electrochemical appliance intercepts positive plate and the direct of negative plate contacts; and provide the ionic conduction passage; inorganic particle plays the mechanical strength that improves laminated film; improve the effect that the laminated film heat resistanceheat resistant is shunk; simultaneously; inorganic particle with high-k also promotes the electrolyte disassociation in the electrolyte of electrochemical appliance, thereby improves the conductivity of electrolyte.And with respect to prior art, organic/inorganic composite porous film of the present invention adopts not and the material of the hydrofluoric acid reaction inorganic particle as active layer, thereby adopts the chemical energy storage device of organic/inorganic composite porous film of the present invention also to have better circulation memory property, high voltage withstanding performance and security performance.
Above-mentioned organic/inorganic composite porous film can adopt all existing making batteries technique of organic/inorganic porous compound film, mainly be that mixture with inorganic particle and adhesive is coated on the porous substrate, make on the inorganic/organic composite porous film of formation and have the hole that is included in the porous substrate self, and form pore structure owing to be formed on the gap between the inorganic particle on the base material in base material and in active layer, so the present invention has the conventional advantage of prior art in principle.
Described porousness organic substrate is the TPO film.
As a kind of improvement of organic/inorganic composite porous film of the present invention, described sulfate is BaSO
4Because BaSO
4Has higher dielectric constant, when adopting BaSO
4During as the inorganic particle in the active layer, it can improve dissociating of electric conducting lithium salt in the electrolyte, thereby improves the conductivity of electrolyte, is conducive to improve the performance of battery.
As a kind of improvement of organic/inorganic composite porous film of the present invention, described phosphate is AlPO
4AlPO
4With respect to Al
2O
3Coating has better cycle performance and overcharging resisting performance.
As a kind of improvement of organic/inorganic composite porous film of the present invention, described metal fluoride is AlF
3, ZnF
2, ZrF
4, among the LiF one or more.In the prior art take oxide as inorganic particle, the product of oxide and hydrofluoric acid is corresponding metal fluoride, and the present invention directly adopts metal fluoride as the inorganic particle in the active layer, therefore so that the stability of organic/inorganic composite porous film is much better than the film that adopts the oxide inorganic particle.
As a kind of improvement of organic/inorganic composite porous film of the present invention, described lithium salts is Li
xPO
yN
z, wherein 0＜x＜7,0＜y＜6,0＜z＜4, and x=2y+3z-5.Inorganic particle Li
xPO
yN
zHave the lithium ion conduction ability, therefore adopt BaSO
4As the inorganic particle in the active layer, can so that lithium ion not only can also can conduct via inorganic particle via the electrolyte conduction in the pore structure of film, help to improve the lithium ion conduction ability in the battery, and then improve the electrical property of battery.
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.
Inorganic/organic composite porous film of the present invention does not have particular restriction to thickness, can carry out according to the actual requirements THICKNESS CONTROL to improve battery performance, and the preferred thickness of film is 1-100 μ m, and optimum thickness is 2-30 μ m.
Consider the thickness limits of inorganic coating and the pore size of barrier film substrate, the particle diameter of described inorganic particle is preferably 0.1-2 μ m.
The pore size of described inorganic/organic composite porous film and porosity depend primarily on the particle diameter of inorganic particle, and for example, when using particle diameter to be 1 μ m or lower inorganic particle, therefore the hole of formation also 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 conducting ion, and therefore, pore size and porosity are the important tired elements of the ionic conductivity of control inorganic/organic composite porous film.Preferably, the pore size of inorganic/organic composite porous film of the present invention and porosity are respectively 0.01-10 μ m and 5-75%.
Inorganic/organic composite porous film of the present invention does not have particular restriction to the mixing ratio of inorganic particle and adhesive, can be according to the two rational proportion of the thickness of the film that finally will form and structure control.
To achieve these goals, the present invention also provides a kind of electrochemical energy storage device, it comprises positive plate, negative plate, electrolyte and the interval barrier film between positive plate and negative plate, and described barrier film adopts the inorganic/organic composite porous film described in the above-mentioned paragraph.
Electrochemical appliance of the present invention can be any device that electrochemical reaction occurs, and such as various primary cells, secondary cell, fuel cell, solar cell or capacitor, is preferably lithium ion battery.
As a kind of improvement of electrochemical energy storage device, above-mentioned inorganic/organic composite porous film and micro-pore septum can also be used micro-pore septum such as polyolefin-based separator together as barrier film.
Electrochemical appliance 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, assemble electrochemical appliance by the inorganic/organic composite porous film that use is inserted between positive plate and the negative plate, then inject 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 inorganic/organic composite porous film of the present invention.Especially, positive electrode active materials can comprise any conventional positive electrode active materials that uses at present in the positive plate of conventional electrochemical appliance, its concrete non-limitative example comprises intercalation materials of li ions, such as lithium manganese oxide, lithium and cobalt oxides, lithium nickel oxide, oxide/lithium ferrite or their composite oxides.In addition, negative active core-shell material can comprise any conventional negative active core-shell material that uses at present in the negative pole of conventional electrochemical appliance, and its concrete non-sex-limited example comprises intercalation materials of li ions, such as lithium metal, lithium alloy, carbon, petroleum coke, active carbon, graphite or carbonaceous material.The non-limitative example of cathode current collector comprises that by aluminium, nickel or its paper tinsel that is combined to form, the non-limitative example of cathodal current current-collector comprises by copper, gold, nickel, copper alloy or its paper tinsel that is combined to form.
The electrolyte that can use in electrochemical appliance of the present invention comprises by formula A
+B
-The salt of expression, wherein A
+Representative is selected from Li
+, Na
+, K
+With the alkali metal cation in their combination, B
-Representative is selected from PF
6 -, BF
4 -, Cl
-, Br
-, I
-, ClO
4 -, ASF
6 -, CH
3CO
2 -, CF
3SO
3 -, N (CF
3SO
2)
2 -, C (CF
2SO
2)
3 -With the anion in their combination, and the salt of dissolving or disassociation in organic solvent.Wherein organic solvent is selected from propene carbonate (PC), carbon vinyl acetate (EC), diethyl carbonate (DEC) dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide (DMSO), acetonitrile, dimethoxy-ethane, oxolane, METHYLPYRROLIDONE (NMP), ethylmethyl carbonate (EMC), r-fourth propyl ester and their mixture.But the electrolyte that can use in the present invention is not limited to above-mentioned example.
Compared with prior art, electrochemical energy storage device of the present invention adopts the more stable organic/inorganic composite porous film of composition as barrier film, therefore has better circulation memory property, high voltage withstanding performance and security performance.
Description of drawings
Below in conjunction with the drawings and specific embodiments, to organic/inorganic composite porous film of the present invention, use the electrochemical energy storage device of this film and useful technique effect thereof to be elaborated.
Fig. 1 is the structural representation of organic/inorganic composite porous film of the present invention.
Fig. 2 is the graph of a relation of the lithium ion battery of embodiment 1 and comparative example 2 capability retention and cycle-index in the time of 60 ℃.
Fig. 3 is that the lithium ion battery of experimental example 1 and comparative example 2 is at 85 ℃ of storage capability retention figure after 48 hours.
Fig. 4 is the discharge-rate Character Comparison figure of the lithium ion battery of experimental example 1 and comparative example 2.
Internal resistance comparison diagram when Fig. 5 is the large multiplying power pulse direct current discharge of the lithium ion battery of embodiment 1 and Comparative Examples 1-2.
Embodiment
See also Fig. 1, inorganic/organic composite porous film of the present invention comprises that the hole on the porousness organic substrate 102(porousness organic substrate 102 is not shown) and be attached to active layer on the porousness organic substrate 102, active layer comprises inorganic particle 104 and binding agent 106.Wherein, porousness organic substrate 102 is the TPO film, inorganic particle 104 is one or more the mixture in sulfate, phosphate, metal fluoride, the lithium salts, bonding agent 106 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.
To organic/inorganic composite porous film of the present invention and use the electrochemical energy storage device of this 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. inorganic/organic composite porous film (BaSO
4Particle) preparation:
In deionized water, add the BaSO that quantity is about 50wt% (solids content metering)
4Powder (D50=1.5 μ m) stirs 1h, then add the PAA-PAAS(Polyacrylic acid-Sodium polyacrylate take solid content meter content as 5wt%, the poly acrylic acid-poly PAA) after the aqueous solution (content of PAA-PAAS in the aqueous solution is 25wt%) stirs 1h, in grinding in ball grinder 1h, add again the CMC solution take solid content meter content as 0.5wt% in the slurry after the grinding, continue to stir 1h, make slurry.Then the above-mentioned slurry that uses reverse roll intaglio plate coating machine to make is coated on the polyethylene micropore film that thickness is 16 μ m (porosity 45%), active layer thickness is that 4 μ m are thick, repeat this step and obtain the thick another side active layer of thickness 4 μ m, namely the gross thickness of composite porous film is 24 μ m.With the composite porous 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
0.5Co
0.2Mn
0.3O
2, 4.0wt% as the carbon black of conductive agent and the PVDF(polyvinylidene fluoride as binding agent of 2.0wt%), 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 rolled (Roll press).
The manufacturing of negative pole: to as adding the powdered graphite as negative electrode active material of 94.5wt%, the carbon black as conductive agent of 2.0wt%, the CMC(sodium carboxymethylcellulose as thickener of 1.5wt% in the deionized water (DI water) of solvent) 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: inorganic/organic composite porous film, positive plate and negative plate that above-mentioned steps makes are reeled together, form battery core; Then (dimethyl carbonate DMC comprises 1M lithium hexafluoro phosphate (LiPF to inject electrolyte in the battery core
6)), obtain lithium ion battery after the encapsulation.
Embodiment 2
2-1. inorganic/organic composite porous film (AlF
3Particle) preparation:
In deionized water, add the AlF that quantity is about 50wt% (solids content metering)
3Powder (D50=1 μ m) stirs 1h, then add the PAA-PAAS aqueous solution and the aqueous silane coupling agent take solid content meter content as 3wt% (3-glycidol ether propyl-triethoxysilicane) 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 1.0wt% in the slurry after the grinding, continue to stir 1h, make slurry.After the surface treatment method that polypropylene microporous film can be improved film surface tension force through corona or other is in advance processed, re-using accurate slit extrusion coating machine will be coated in such as the slurry that above-mentioned method makes on the polypropylene microporous film that thickness is 20 μ m (porosity 48%), active layer thickness is that 5 μ m are thick, repeat this step and obtain the thick another side active layer of thickness 5 μ m, namely the gross thickness of composite porous film is 30 μ m.The porosity of the composite porous 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 inorganic/organic composite porous film that adopts present embodiment to make.
Embodiment 3
3-1. the preparation of inorganic/organic composite porous film (AlPO4)
In deionized water, add the AlPO that quantity is about 50wt% (solids content metering)
4Powder (D50=1.3 μ m) stirs 1h, then add the PAA-PAAS aqueous solution and silane coupler (3-glycidol ether propyl trimethoxy silicane) take solid content meter content as 3wt% 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.Use reverse roll intaglio plate coating machine will be coated in such as the slurry that above-mentioned method makes on the polypropylene microporous film that thickness is 16 μ m (porosity 45%), active layer thickness is that 4 μ m are thick, repeat this step and obtain the thick another side active layer of thickness 4 μ m, namely the gross thickness of composite porous film is 24 μ m.The porosity of measuring composite porous film with mercury injection apparatus is about 42%.
3-2. the manufacturing of lithium ion battery: step is identical with embodiment 1, and difference only is the inorganic/organic composite porous film that adopts present embodiment to make.
Embodiment 4
4-1. inorganic/organic composite porous film (BaSO
4/ AlF3 hybrid particles) preparation
In deionized water, add the BaSO that quantity is about 15wt% (solids content metering)
4And the AlF of 15wt% (solids content metering)
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 use reverse roll intaglio plate coating machine will be coated in such as the slurry that above-mentioned method makes on the polyethylene micropore film that thickness is 16 μ m (porosity 45%), active layer thickness is that 3 μ m are thick, repeat this step and obtain the thick another side active layer of thickness 3 μ m, namely the gross thickness of composite porous film is 22 μ m.The porosity of measuring composite porous film with mercury injection apparatus is 44%, with the basic indifference of polyethylene micropore film porosity.
4-2. the manufacturing of lithium ion battery: step is identical with embodiment 1, and difference only is the inorganic/organic composite porous film that adopts present embodiment to make.
Embodiment 5
5-1. inorganic/organic composite porous film (Li
2.98PO
3.3N
0.46Particle) preparation
In deionized water, add the Li that quantity is about 50wt% (solids content metering)
2.98PO
3.3N
0.46Powder (D50=1.6 μ m) stirs 1h, then add the PAA-PAAS aqueous solution and silane coupler (3-glycidol ether propyl trimethoxy silicane) take solid content meter content as 3wt% 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.After the surface treatment method that polypropylene microporous film can be improved film surface tension force through corona or other is in advance processed, use reverse roll intaglio plate coating machine will be coated in such as the slurry that above-mentioned method makes on the polypropylene microporous film that thickness is 20 μ m (porosity 48%), active layer thickness is that 4 μ m are thick, repeat this step and obtain the thick another side active layer of thickness 4 μ m, namely the gross thickness of composite porous film is 28 μ m.The porosity of measuring composite porous film with mercury injection apparatus is about 44%.
5-2. the manufacturing of lithium ion battery: step is identical with embodiment 1, and difference only is the inorganic/organic composite porous film that adopts present embodiment to make.
Comparative example 1
Method according to embodiment 1 prepares positive plate, negative plate, and uses conventional polythene PE barrier film to make lithium ion battery.Barrier film has about 45% porosity.
Comparative example 2
Method according to embodiment 1 prepares positive plate, negative plate and organic/inorganic composite film, but changes inorganic particle into Al2O3, makes lithium ion battery.
Inorganic/organic composite porous film of the present invention below is described by experiment and uses the performance of the lithium ion battery of this film.
Experiment 1: the thermal contraction assessment of inorganic/organic composite porous film
The inorganic/organic composite porous film that this experiment use embodiment 1 obtains is as sample, and the PE barrier film of usage comparison example 1 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 comparative example 1 PE barrier film in contrast, and become transparent, microcellular structure merges; By contrast, the inorganic/organic composite porous film of the embodiment of the invention 1 obvious micropore do not occur and merges, and thermal contraction is very little.As seen, inorganic/organic composite porous film of the present invention has good thermal stability.
Experiment 2: safety of lithium secondary battery assessment
Experiment 2-1. drift bolt test: the lithium rechargeable battery sample of embodiment 1 to 4 and the lithium rechargeable battery sample of comparative example 1 completely are charged to respectively 4.2V, and after leaving standstill 1 hour, measuring voltage and resistance, iron nail with diameter 5mm penetrates each battery sample, while monitoring battery surface temperature, the situation of observing each battery sample.The result shows, the lithium secondary battery of embodiment 1 to 4 is not smoldered and not on firely do not exploded, and battery is very safe; And the control sample of comparative example 1, it is on fire to occur obviously smoldering.As seen, use the lithium secondary battery of inorganic/organic composite porous film of the present invention to have the Good Security that can prevent that battery is on fire and explode.
Experiment 2-2. overcharges test: the lithium rechargeable battery sample of embodiment 1 to 4 and the lithium rechargeable battery sample of comparative example 1 are discharged to respectively 3.0V, and the electric current that re-uses 1C is crossed and is charged to 6.0V and kept the situation of observing each battery sample 2.5 hours.The result shows, the lithium rechargeable battery sample of embodiment 1 to 4 do not smolder, not on fire, do not explode, smoldering then appears in the lithium rechargeable battery sample of comparative example 1, phenomenon on fire.Test result shows, adopts the lithium rechargeable battery of inorganic/organic composite porous film of the present invention to have good overcharging resisting security performance.
The hot case of experiment 2-3. test: the lithium rechargeable battery sample of the lithium rechargeable battery sample of embodiment 1 to 4 and comparative example 1 completely is charged to respectively 4.2V and left standstill 1 hour, each battery sample was placed 150 ℃ of hot casees 1 hour, then check battery.Check result shows, the lithium rechargeable battery sample of embodiment 1 to 4 do not smolder, not on fire, also do not explode; And the lithium rechargeable battery sample of comparative example 1 is all blasted.As seen, adopt the lithium secondary battery of inorganic/organic composite porous film of the present invention to show the safe condition that can prevent that battery is on fire and burn.
Experiment 2-4. bump test: the lithium rechargeable battery sample of embodiment 1 to 4 and the lithium rechargeable battery sample of comparative example 1 completely are charged to respectively 4.2V, use diameter as the height bump battery center of ear of maize 61cm above battery of 15.8mm, heavy 9.1Kg, check battery.The result shows, the lithium rechargeable battery sample of embodiment 1 to 4 do not smolder, not on fire, also do not explode; And the lithium rechargeable battery sample of comparative example 1 each smolder on fire.Illustrate that the lithium secondary battery that adopts inorganic/organic composite porous film of the present invention shows the safe condition that can prevent that battery is on fire and burn.
Experiment 2-5. squeeze test: the lithium rechargeable battery sample of embodiment 1 to 4 and the lithium rechargeable battery sample of comparative example 1 completely are charged to 4.2V, between two flat boards, push, until pressure reaches release pressure behind the 13KN, observe battery.The result shows, the lithium rechargeable battery sample of embodiment 1 to 4 do not smolder, not on fire, also do not explode; And the lithium rechargeable battery sample of comparative example 1 each smolder on fire.Illustrate that the lithium secondary battery that adopts inorganic/organic composite porous film of the present invention shows the safe condition that can prevent that battery is on fire and burn.
Experiment 3: the cycle performance evaluation of lithium ion battery
The use BaSO of employed sample for obtaining according to embodiment 1 in this experiment
4The lithium ion battery of/PAA-PAAS polyethylene laminated film, and the use Al of usage comparison example 2
2O
3The lithium ion battery of/PAA-PAAS composite diaphragm in contrast.The relation of the lithium ion battery of shown in Figure 2 is embodiment 1, embodiment 3 and comparative example 2 capability retention and cycle-index in the time of 60 ℃, as we can see from the figure, the cycle performance of lithium ion battery of the embodiment of the invention 1 and embodiment 3 obviously is better than the battery of comparative example 2.
Experiment 4: the memory property evaluation of lithium ion battery
The sample of this experiment is the lithium ion battery of embodiment 1 and comparative example 2, and 85 ℃ of storages after 48 hours, the battery of comparative experiments example 1 and comparative example 2 is through the capability retention after the storage with battery.As shown in Figure 3, the battery capacity of the embodiment of the invention 1 only decays 1%, and the battery capacity of comparative example 2 decay 4%, and 4 times of capacity attenuations are to battery of the present invention.
Experiment 5: the high rate performance evaluation of lithium ion battery
This experiment uses the lithium ion battery of embodiment 1 as sample, and the battery of usage comparison example 2 in contrast.As shown in Figure 4, experimental result shows, adopts the lithium ion battery of inorganic/organic composite porous film of the present invention to show than using Al
2O
3The better discharge-rate characteristic of the lithium ion battery of/PAA-PAAS composite diaphragm.
Experiment 6: the DC internal resistance evaluation of lithium ion battery
The sample of this experiment is the lithium ion battery of embodiment 1, Comparative Examples 1 and 2, 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 cell of the present invention is lower than the battery 10%-20% of comparative example 2, and also is lower than comparative example 1.
Experiment 7: high voltage withstanding performance evaluation
This experiment uses the lithium secondary battery of embodiment 1 as sample, and the battery of usage comparison example 2 in contrast.The flow process of experiment is: the battery of experimental example 1 and comparative example 2 is charged to 4.5V and under 4.5V constant voltage kept one hour, then disassemble the state that battery core is observed laminated film.The result shows that inorganic/organic composite porous film of the present invention does not have the recurring structure variation, and uses Al under the same terms after the high voltage oxidation of experience 4.5V
2O
3The inorganic active layer of the laminated film of inorganic particle has occured to come off.As seen, laminated film of the present invention shows more outstanding high voltage withstanding performance, can be applied to the lithium ion battery of high voltage system.
The according to the above description announcement of book and instruction, 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. organic/inorganic composite porous film, it comprises porousness organic substrate and the active layer that is attached on the porousness organic substrate, active layer comprises inorganic particle and binding agent, it is characterized in that: described inorganic particle is one or more the mixture in sulfate, phosphate, metal fluoride, the lithium salts.
2. organic/inorganic composite porous film according to claim 1, it is characterized in that: described sulfate is BaSO
4, phosphate is AlPO
4, metal fluoride is AlF
3, ZnF
2, ZrF
4, among the LiF one or more, lithium salts is Li
xPO
yN
z, wherein 0＜x＜7,0＜y＜6,0＜z＜4, and x=2y+3z-5.
3. organic/inorganic composite porous film according to claim 1, it is characterized in that: the particle diameter of described inorganic particle is preferably 0.1-2 μ m.
4. organic/inorganic composite porous film according to claim 1, it is characterized in that: the pore size of described inorganic/organic composite porous film is 0.01-10 μ m, and porosity is 5-75%.
5. organic/inorganic composite porous film according to claim 1, it is characterized in that: the thickness of described film is 1-100 μ m, is preferably 2-30 μ m.
6. organic/inorganic composite porous film according to claim 1, it is characterized in that: described porousness organic substrate is the TPO film.
7. organic/inorganic composite porous film according to claim 1, it is characterized in that: 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.
8. electrochemical energy storage device, it comprises positive plate, negative plate, electrolyte and the interval barrier film between positive plate and negative plate, it is characterized in that: described barrier film adopts each described inorganic/organic composite porous film among the claim 1-7.
9. electrochemical energy storage device according to claim 8, it is characterized in that: described barrier film also comprises the polyolefin-based separator of using with the inorganic/organic composite porous film.
10. electrochemical energy storage device according to claim 8, it is characterized in that: described electrochemical energy storage device is primary cell, secondary cell, fuel cell, solar cell or capacitor, is preferably lithium ion battery.
Priority Applications (1)
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