CN102719046A - Ionic polymer/ceramic composite membrane material, preparation method thereof and lithium secondary battery - Google Patents
Ionic polymer/ceramic composite membrane material, preparation method thereof and lithium secondary battery Download PDFInfo
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- CN102719046A CN102719046A CN2012102195908A CN201210219590A CN102719046A CN 102719046 A CN102719046 A CN 102719046A CN 2012102195908 A CN2012102195908 A CN 2012102195908A CN 201210219590 A CN201210219590 A CN 201210219590A CN 102719046 A CN102719046 A CN 102719046A
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Abstract
The invention relates to an ionic polymer/ceramic composite membrane material, a preparation method thereof and a lithium secondary battery and belongs to the field of manufacturing of lithium batteries. The ionic polymer/ceramic filler composite membrane material is a pore-free dense membrane which is formed by a ceramic filler and a polymer colloidal particle which has a sulfonate group on the surface, and an evident thermal contraction can not happen to a diaphragm after a battery is overheated. When an ionic polymer/ceramic filler composite membrane absorbs an electrolyte, a penetrating ionic conduction path is formed among colloidal particles, and after the ionic polymer/ceramic filler composite membrane absorbs the electrolyte solution or a solvent, a colloid particle structure is still maintained. By means of the dense stacking of sphere structures of the colloidal particles and ceramic filler particles which are uniformly distributed in the membrane, the sinuosity of the ionic conduction path is increased, an electronic insulation performance of a polymer electrolyte membrane is improved, simultaneously the rigidity of the ionic polymer membrane is improved due to the presence of the ceramic filler particles, and the deformation of the ionic polymer membrane is reduced.
Description
Technical field
The present invention relates to be used for diaphragm material of energy storage device such as lithium-ion secondary cell and preparation method thereof, belong to lithium cell and make the field.
Background technology
Battery is made up of positive pole, negative pole, barrier film and electrolytic solution.Barrier film is that significant components is one of former in battery; Its effect in battery is as the barrier film between the inside battery positive and negative electrode; Prevent that the direct contact of positive and negative electrode from causing internal short-circuit, the while completely cuts off electronics again and guarantees smooth and easy the passing through of ion in the electrolytic solution, with the electrochemical reaction of support cells.
Present commercial lithium ion battery, lithium metal secondary battery, the employed battery isolating film of lithium-sulfur cell mainly is a MIcroporous polyolefin film.The polyolefin micropore film manufacturing method has two kinds of technological lines: a kind of is the dry technique route; Another kind is the Wet technique route.No matter can find out from the MIcroporous polyolefin film ME, be dry method or wet method, all will carry out mechanical stretching before the pore-forming, and used polyolefin resin is Vestolen PP 7052 (PP) or Vilaterm (PE) non-polar material.Owing to PP or PE material inherent chemistry and reasons such as physical property and microporous membrane ME, guaranteeing that MIcroporous polyolefin film also exists performance deficiency aspect lithium ion battery security and work-ing life.
The subject matter that MIcroporous polyolefin film exists: the one, the imbibition and the liquid-keeping property of microporous membrane are poor; PP or PE are a kind of non-polar materials; It is poor with strong polar electrolyte solution affinity; The absorption that the affinity that electrolytic solution and MIcroporous polyolefin film are lower has caused microporous membrane with keep the electrolytic solution ability, and the imbibition of microporous membrane and liquid-keeping property power have close dependency work-ing life to the charge and discharge cycles of battery; The 2nd, microporous membrane film poor heat stability because MIcroporous polyolefin film is through the mechanical stretching pore, or is used the organic solvent extraction pore again behind the mechanical stretching; And passing through the microporous membrane that heat setting type makes, this preparation technology makes microporous membrane have residual stress, makes microporous membrane have SME; After the polyolefin resin heating temperature was near softening temperature, microporous membrane had the shape before being tending towards recovering to stretch, and produced bigger contraction; The microporous membrane thermal contraction must be followed volumetric shrinkage, and membrane area dwindles phenomenon and takes place, and makes the microporous membrane iris action between positive and negative that scatters and disappears; Thereby the inside battery positive and negative electrode is short-circuited, causes safety issues such as battery burning, blast.
Performance deficiency based on the MIcroporous polyolefin film existence; And the origin cause of formation of these performance deficiencies of generation; Contriver of the present invention had once proposed a kind of lithium ion battery separator (one Chinese patent application CN 102280605A) that heat expansion merges blackout effect that has, and this film comprises that micropore polyolefin barrier diaphragm and its surface coverage the polymeric colloid particle coating that particle diameter is 10-1000nm.Said polymeric colloid particle coating is the surface that is coated on micropore polyolefin barrier diaphragm by the vinyl cyanide polymer latex precursor emulsion that polymerization forms in the organic solvent of EVA, and dry back forms.
Subsequently, the inventor has proposed to have the ionic polymer mould material that the acrylic polymer colloidal particle of sulfonate groups constitutes by the surface.
This material need not mechanical stretching, there do not have to be stress-retained, with electrolytic solution fine affinity (one Chinese patent application 201210181362.6 of application on June 4th, 2012) is arranged.Contriver of the present invention finds under study for action; 201210181362.6 use acrylic polymer to be filmogen in number patented claim; Prepared ionic polymer membranes snappiness is better; And rigidity is not enough, in use produces bigger deformation, has influenced the application of ionic polymer membranes in lithium ion battery.
The present invention is on the basis of No. 201210181362.6 patented claims, through in ionic polymer membranes, adding ceramic packing, processes ionic polymer/ceramic composite membrane, to improve the rigidity of ionic polymer membranes, reduces the deformation of ionic polymer membranes.
Summary of the invention
Technical problem to be solved by this invention is: a kind of ionic polymer/ceramic packing composite film material is provided.
Technical scheme of the present invention: ionic polymer provided by the invention/ceramic packing composite film material is to be made up of polymeric colloid particle and ceramic packing that the surface has a sulfonate groups.It is a kind of imporous dense film, when the overheated metacneme of battery can not produce tangible thermal contraction.
Ionic polymer mould material of the present invention preferably, the acrylic polymer colloidal particle that is had sulfonate groups by the surface constitutes, and has guaranteed that ionic polymer mould material of the present invention and electrolytic solution have intermiscibility preferably.
Ionic polymer mould material of the present invention is in polymerization process, is emulsifying agent with the response type sulfosalt surfactant, and synthetic surface has the acrylic polymer colloid emulsion of sulfonate groups.In this polymer latex precursor emulsion, add the ceramic packing slurry, fully be uniformly dispersed after casting film-forming forms the ionic polymer/ceramic packing composite package with maintenance colloidal particle structure.Form the ionic conduction path that connects behind ionic polymer/ceramic packing composite package Electolyte-absorptive between colloidal particle and colloidal particle, and behind absorbed electrolyte solution or the solvent, this composite film material can still keep the colloidal particle structure.The dense accumulation of colloidal particle sphere structure, and be dispersed in the ceramic packing particle in the film, increased the tortuosity of ionic conduction path, improved the electronic isolation performance of polyelectrolyte film.Simultaneously, the existence of ceramic packing particle has improved the rigidity of ionic polymer membranes, reduces the deformation of ionic polymer membranes.
As the preferred scheme of the present invention, the average particle size range of colloidal particle is 10nm～1.0 μ m, the average particle size range 10nm of ceramic packing particle～5.00 μ m; Preferably, the average particle size range of colloidal particle is 20～200nm, the average particle size range 20nm of ceramic packing particle～0.5 μ m; More preferably 20nm～200nm.
Ceramic packing particle shared mass percent in film is 10-60%.Preferably 15-50%, more preferably 25-30%.
The thickness of said ionic polymer/ceramic packing composite package is 10～40 μ m.
Ionic polymer provided by the invention/ceramic packing composite package is to be prepared from following method:
1. the polymer latex precursor emulsion is synthetic: colloid protective agent and zero(ppm) water are joined in the reaction flask; Heated and stirred is up to dissolving fully; Add response type sulfosalt surfactant, polymerization reaction monomer and linking agent (random order) and mix, add the initiator polyreaction then and obtain the polymer latex precursor emulsion;
2. the preparation of ceramic packing slurry: in zero(ppm) water, add ceramic packing and dispersion agent, after being uniformly dispersed, with ball mill dispersions of further milling, cross 200 purposes sieve and both get again with the material of removing not fine ground larger particles.
3. with the ceramic packing slurry that adds step 2 preparation in the polymer latex precursor emulsion of step 1 preparation; Be coated in after being uniformly dispersed on the plastics base band, like PET (polyethylene terephthalate) base band, behind oven dry moisture; Peel off, promptly get ionic polymer/ceramic packing composite package.
Ceramic packing shared mass percent in ionic polymer/ceramic packing composite package is 10-60%.15-50% preferably.
Said response type sulfosalt surfactant is that one or more mixing in vinylsulfonate, allylsulfonate, methallylsulfonic acid salt, allyloxy hydroxypropyl sulphonate, hydroxyethyl methacrylate propyl sulfonic acid salt, 2-acrylamido-2-methyl propane sulfonic acid salt, the styrene sulfonate are used; Wherein, positively charged ion is lithium ion, sodium ion or potassium ion, and consumption is 2～10% of a polymerization reaction monomer gross weight.。
The described colloid protective agent of step 1 is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably Z 150PH.The consumption of colloid protective agent is 5～30% of a polymerization reaction monomer gross weight, preferably 10～25%.
The said dispersion agent of step 2 is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably polyethylene alcohol.In the said ceramic packing slurry, the content of ceramic packing is 80～95%, the content 5～20% of dispersion agent, and solid content of slurry is 20～50%.
As the preferred scheme of the present invention is that said polymerization single polymerization monomer is a methyl acrylate, and methyl acrylate content is 40～80% in polymeric colloid
For the heat-shrinkable of adjusting mould material, to the imbibition liquid-keeping property of electrolytic solution and snappiness of telomerized polymer or the like, the further preferred scheme of the present invention is also to add second kind of polymerization single polymerization monomer CH in the polymerization reaction system
2=CR
1R
2Carry out polyreaction;
Wherein, R
1=-H or-CH
3R
2=-C
6H
5,-OCOCH
3,-CN ,-C
4H
6ON ,-C
2H
3CO
3,-COO (CH
2) nCH
3, n is 0～14.
Second kind of monomer is any one or more mixing use in the above-mentioned monomer, and its consumption is 2～10% of a polymerization single polymerization monomer gross weight.
Described linking agent is to contain two two keys or two above polymerisable monomers of two keys; Like divinylbenzene, Viscoat 295, adipic acid two propylene esters, methylene-bisacrylamide etc., its consumption is 2.0～10.0% of a polymerization reaction monomer gross weight.
Described initiator is water soluble starters such as ammonium persulphate, Potassium Persulphate, hydrogen peroxide, azo two NSC 18620s, and its consumption is 0.2～1.0% of a monomer weight.
As the preferred scheme of the present invention be the raw material of polyreaction: response type sulfosalt surfactant, polymerization reaction monomer and linking agent are once to add, drip or add step by step to react.Polymerization reaction monomer described herein is methacrylate monomer or the methacrylate monomer and the second monomeric combination.
Further preferably, add earlier the raw material (by weight) of 1/5～1/3 polyreaction, drip again behind the polyreaction certain hour or substep adds the raw material of remaining polyreaction.
Polymerization reaction time reaches more than 92% with the transformation efficiency of monomer polymerization reactions is advisable.Usually 4-36 hour was good with 8～24 hours.
Polymeric reaction temperature is 50～90 ℃, is good with 55～70 ℃.
Described ceramic packing is MOX and composite oxide of metal, and its general formula is NzMxOy, and wherein N is basic metal or alkali earth metal, and M is a metallic element, and Z is 0～5, and x is 1～6, and y is 1～15.Ceramic packing median size (D50) is 10nm～5.0 μ m, preferred 20nm～0.5 μ m, and preferred ceramic packing is Al
2O
3, median size (D50) is 20nm～200nm.
Beneficial effect of the present invention
The invention provides a kind of production technique simple, cheap for manufacturing cost, be that dispersion medium is environmentally friendly, pollution-free, the preparation method of the lithium ion battery of environmental protection ionic polymer/ceramic packing composite package with water.
Ionic polymer of the present invention/ceramic packing composite film material is that acrylic polymer colloidal particle and mineral filler constitute; The SP of the SP of acrylic polymer and electrolytic solution organic solvent is close; Guaranteed that ionic polymer/ceramic packing composite package and electrolytic solution have intermiscibility preferably; Reach good imbibition and liquid-keeping property, can improve battery and recycle the life-span.
Ionic polymer/ceramic packing composite package is adopt that polymeric colloid emulsion curtain coating film-forming process makes unstressed residual and is dispersed in a kind of imporous dense film that the ceramic packing particle in the film constitutes by colloidal particle; Barrier film does not have tangible thermal contraction when battery is overheated, thereby can prevent the short circuit of inside battery positive and negative electrode.
Form the ionic conduction path that connects behind ionic polymer/ceramic packing composite package Electolyte-absorptive between colloidal particle and colloidal particle, and behind absorbed electrolyte solution or the solvent, this composite film material can still keep the colloidal particle structure.The dense accumulation of colloidal particle sphere structure, and be dispersed in the ceramic packing particle in the film, increased the tortuosity of ionic conduction path, improved the electronic isolation performance of polyelectrolyte film.Simultaneously, the existence of ceramic packing particle has improved the rigidity of ionic polymer membranes, reduces the deformation of ionic polymer membranes.
Description of drawings
Fig. 1 is the ionic polymer membranes and the ionic polymer/Al of embodiment 1 and embodiment 6 preparations
2O
3The lithium cell discharge curve contrast of composite package, ordinate zou is voltage (V), and X-coordinate is gram volume (mAh/g), and a is ionic polymer/Al
2O
3Compound film battery, b are the ionic polymer film battery.
Fig. 2 is ionic polymer/Al
2O
3Lithium cell the 5th of composite package and the 100th charging and discharging curve, ordinate zou is voltage (V), and X-coordinate is gram volume (mAh/g), and A is the 5th charging and discharging curve, and B is the 100th charging and discharging curve.
Fig. 3 is the ionic polymer/Al of embodiment 6 preparations
2O
3The ESEM picture of composite package.
Below through the mode of specific embodiment the present invention is done further detailed description, but do not represent the present invention to implement with following mode.
Embodiment
The present invention provides a kind of ionic polymer/ceramic packing composite film material, is to be made up of acrylic polymer colloidal particle and ceramic packing that the surface has a sulfonate groups.Said polymkeric substance preferably with the close acrylic polymer of electrolytic solution solvent for use SP; Ionic polymer/strong the polar group on ceramic packing composite package colloidal particle surface and the super solvent of nonaqueous electrolyte can form the chemical association effect simultaneously; Guaranteed that ionic polymer mould material of the present invention and electrolytic solution have intermiscibility preferably, reach good imbibition and liquid-keeping property.
As the preferred scheme of the present invention, the average particle size range that the surface has the polymeric colloid particle of sulfonate groups is 10nm～1.0 μ m, the particle size range 10nm of ceramic packing particle～5.00 μ m; Preferably, the average particle size range of colloidal particle is 20～200nm, the average particle size range 20nm of ceramic packing particle～0.5 μ m; More preferably 20nm～200nm.
Ionic polymer provided by the invention/ceramic packing composite package is to be prepared from following method:
1. at first synthetic surface contains the polymer latex precursor emulsion of anionic group, and colloid protective agent and zero(ppm) water are joined in the reaction flask, and heated and stirred is up to dissolving fully; Again that temperature of reactor is constant in 50～90 ℃ of desired reaction temperatures; With 60～70 ℃ is good; Once add response type sulfosalt surfactant and methyl acrylate and second kind of monomer and linking agent; Add the initiator initiated polymerization then, also can add 1/5～1/3 response type sulfosalt surfactant and methyl acrylate earlier, drip subsequently or substep adds remaining response type sulfosalt surfactant and methyl acrylate and second kind of monomer and linking agent; Polyreaction 4～36 hours was good with 8～24 hours.
2. the preparation of pre-dispersed ceramic packing slurry; In zero(ppm) water, add a ceramic packing and a part dispersion agent; After dispersed with stirring is even; Adopt the agitating ball mill dispersion of further milling again, the jitter time of milling plumage 2～10 hours, preferred 3～5 slurries after milling for a short time are again through < 200 purpose screen filtrations are to remove the material of not fine ground larger particles.
3. will synthesize the pre-dispersed good ceramic packing slurry that adds specified amount in the good polymer latex precursor emulsion; The mixture of polymer latex precursor emulsion and ceramic packing slurry adopts the abundant dispersed with stirring of dispersed with stirring equipment even again; Adopt the curtain coating coating process to be coated on the plastics base band then, like PET (polyethylene terephthalate) base band, behind oven dry moisture; Peel off, promptly get ionic polymer/ceramic packing composite package.
Said response type sulfosalt surfactant is that one or more mixing in vinylsulfonate, allylsulfonate, methallylsulfonic acid salt, allyloxy hydroxypropyl sulphonate, hydroxyethyl methacrylate propyl sulfonic acid salt, 2-acrylamido-2-methyl propane sulfonic acid salt, the styrene sulfonate are used; Wherein, positively charged ion is lithium ion, sodium ion or potassium ion, and consumption is 2～10% of a polymerization reaction monomer gross weight.
The described colloid protective agent of step 1 is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably Z 150PH.The consumption of colloid protective agent is 5～30% of a polymerization reaction monomer gross weight, preferably 10～25%.
The said ceramic packing dispersion agent of step 2 is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably polyethylene alcohol.In the said ceramic packing slurry, the content of ceramic packing is 80～95%, the content 5～20% of dispersion agent, and solid content of slurry is 20～50%.
As methyl acrylate content in the polymeric colloid of preferred version of the present invention is 40～80%.
Said second kind of polymerization single polymerization monomer is CH
2=CR
1R
2, wherein, R
1=-H or-CH
3R
2=-C
6H
5,-OCOCH
3,-CN ,-C
4H
6ON ,-C
2H
3CO
3,-COO (CH
2) nCH
3, n is 0～14.
Second kind of monomer is any one or more mixing use in the above-mentioned monomer, and its consumption is 2～10% of a polymerization reaction monomer gross weight.
Described linking agent is to contain two two keys or two above polymerisable monomers of two keys, and like divinylbenzene, Viscoat 295, adipic acid two propylene esters, methylene-bisacrylamide etc., its consumption is 2.0～10.0% of a monomer weight.
Described initiator is water soluble starters such as ammonium persulphate, Potassium Persulphate, hydrogen peroxide, azo two NSC 18620s, and its consumption is 0.2～1.0% of a monomer weight.
As the preferred scheme of the present invention be the raw material of polyreaction: response type sulfosalt surfactant, polymerization reaction monomer and linking agent are once to add, drip or add step by step to react.Polymerization reaction monomer described herein is methacrylate monomer or the methacrylate monomer and the second monomeric combination.
Further preferably, add earlier the raw material (by weight) of 1/5～1/3 polyreaction, drip again behind the polyreaction certain hour or substep adds the raw material of remaining polyreaction.
Described ceramic packing is MOX and composite oxide of metal, and its general formula is NzMxOy, and wherein N is basic metal or alkali earth metal, and M is a metallic element, and Z is 0～5, and x is 1～6, and y is 1～15.Such as: Al
2O
3, SiO
2, Li
4Ti
5O
12
Ceramic packing median size (D50) is preferably 10nm～5.0 μ m, better is 20nm～0.5 μ m, and preferred ceramic packing is Al
2O
3, median size (D50) is 20nm～200nm.
Embodiment 1 does not contain the comparative film of ceramic packing
Synthesizing of polymer latex precursor emulsion: in the four-hole reaction vessel of band water of condensation; Add the 1000g zero(ppm) water and the polymerization degree and be 1700, degree of hydrolysis is 99% Z 150PH 51g, is warming up to 92 ℃ then, stirring and dissolving; Treat that Z 150PH dissolves postcooling to 60 ℃ fully; Add 156g methyl acrylate (MA) monomer, 10g allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) and 10g linking agent methylene-bisacrylamide and stir 1h, add 2g ammonium persulphate initiated polymerization, after reaction is carried out 6 hours; Add 100g (MA) and 5gAHPS again; Add the 1.5g ammonium persulphate simultaneously and continue polymerization 10 hours, get the polymer latex precursor emulsion of the white of solid content 23.9%, the monomer turnover ratio reaches 96%.
Institute's synthetic polymer latex precursor emulsion, the colloidal particle median size (D50) that adopts laser particle size analyzer to measure is 1.62 μ m.
The polymer latex precursor emulsion of preparation is coated on the PET base band, and behind the oven dry moisture, getting thickness is the ionic polymer membranes of 20 ~ 25 μ m, as the comparative film of not adding ceramic packing.
The ceramic packing slurry that following examples adopt prepares through following method:
Al
2O
3The preparation of slurry: in 1000 parts of zero(ppm) water, add the polymerization degree and be 1700, degree of hydrolysis is 20 parts of 99% Z 150PH; Be heated to 90 ~ 94 ℃ then; Under agitation dissolve polyvinyl alcohol is 3 hours, is cooled to room temperature subsequently and adds 200 parts of median sizes (D50) again and be the Al of 36nm
2O
3, dispersed with stirring evenly after, adopt the agitating ball mill dispersion of further milling again, the jitter time of milling is 4 hours, the slurry after milling passes through again<200 purpose screen filtrations are to remove the material of not fine ground larger particles.
At Al
2O
3In the slurry course of processing, because of Al in the slurry that finally obtains is run off in the volatilization of moisture
2O
3Content be 21.5%.
The preparation of embodiment 2 ionic polymers/ceramic packing composite package
Get polymer latex precursor emulsion 100g, Al
2O
3Slurry 12.4g placed the there-necked flask churning time 10 hours,, must disperse homogeneous polymer colloid emulsion and Al
2O
3The slurry mix slurry adopts the curtain coating coating process that mixture paste is coated on PET (polyethylene terephthalate) base band then, behind oven dry moisture, peels off, and getting thickness is ionic polymer/Al of 20 ~ 25 μ m
2O
3Composite package, wherein, Al
2O
3Shared mass percent is 10% in film.
The preparation of embodiment 3 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 19.6g that slurry adds, wherein, and Al
2O
3Shared mass percent is 15% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 4 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 27.8g that slurry adds, wherein, and Al
2O
3Shared mass percent is 20% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 5 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 37.1g that slurry adds, wherein, and Al
2O
3Shared mass percent is 25% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 6 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 47.6g that slurry adds, wherein, and Al
2O
3Shared mass percent is 30% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 7 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 74.1g that slurry adds, wherein, and Al
2O
3Shared mass percent is 40% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 8 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 111.2g that slurry adds, wherein, and Al
2O
3Shared mass percent is 50% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
The preparation of embodiment 9 ionic polymers/ceramic packing composite package
Present embodiment ionic polymer/Al
2O
3The method for making of composite package is same as embodiment 2, uniquely different is Al
2O
3It is to be 166.7g that slurry adds, wherein, and Al
2O
3Shared mass percent is 60% in film, ionic polymer/Al
2O
3Composite package thickness is 20 ~ 25 μ m.
Test Example 1
Ionic polymer/Al that embodiment 1～9 is made
2O
3Composite package is immersed in the electrolyte solution of NSC 11801/diethyl carbonate/methylcarbonate and LiPF6 composition; After treating the abundant absorbed electrolyte solution of composite package; Measure the electrolyte solution absorbed dose, and use the electrochemical impedance appearance to measure its ionic conductivity, test result is listed in table 1.
Test Example 2
Ionic polymer/Al that embodiment 1～9 is made
2O
3Composite package is heated to 130 ℃, measures its percent thermal shrinkage, and test result is listed in table 1.
Table 1. ionic polymer/Al
2O
3Electrolytic solution absorbed dose, ionic conductivity and the percent thermal shrinkage of composite package
| The barrier film kind | Al 2O 3% | Electrolytic solution absorbed dose % | Specific conductivity Scm -1 | 130 ℃ of shrinking percentage % |
| Embodiment 1 | 0 | 111.9 | 2.1×10 -4 | 2.65 |
| Embodiment 2 | 10 | 124.5 | 2.38×10 -4 | 2.45 |
| Embodiment 3 | 15 | 131.9 | 2.66×10 -4 | 2.15 |
| Embodiment 4 | 20 | 145.9 | 2.69×10 -4 | 1.75 |
| Embodiment 5 | 25 | 150.9 | 3.16×10 -4 | 1.75 |
| Embodiment 6 | 30 | 151.5 | 4.28×10 -4 | 1.45 |
| Embodiment 7 | 40 | 131.5 | 2.52×10 -4 | 1.25 |
| |
50 | 129.6 | 2.05×10 -4 | 1.00 |
| Embodiment 9 | 60 | 109.5 | 1.78×10 -4 | 0.65 |
The data of table 1 show ionic polymer/Al of the present invention
2O
3Composite package is with Al
2O
3The increase percent thermal shrinkage reduce gradually, specific conductivity presents optimum value at ceramic packing about 30%, after ceramic packing content surpassed 50%, specific conductivity descended thereupon.Therefore, show that the content of ceramic packing should not surpass 60% from above data.Preferably 15-50%, more preferably 25-30%.
Test Example 3
With ionic polymer and the ionic polymer/Al of embodiment 1 with embodiment 6 preparations
2O
3Composite package is assembled into 2032 button cells by the button cell preparation technology that industry technician all is familiar with, and this battery is with LiMn
2O
4Be positive electrode material, metallic lithium is that the electrolyte solution that negative material and NSC 11801/diethyl carbonate/methylcarbonate/LiPF6 form constitutes, and 2032 button lithium batteries carry out the charge-discharge performance test under 0.2C multiplying power condition.
Fig. 1 is the ionic polymer membranes and the ionic polymer/Al of embodiment 1 and embodiment 6 preparations
2O
3The lithium cell discharge curve of composite package, it shows ionic polymer/Al
2O
3Composite package has better charge-discharge performance than ionic polymer membranes, and under the same conditions, the gram volume of the battery lithium manganate material of ionic polymer membranes has only 107mAh/g, and ionic polymer/Al
2O
3The gram volume of the battery lithium manganate material of composite package reaches 115mAh/g.The raising of lithium manganate material gram volume be help Al
2O
3And the existence at the out-phase interface between polymeric colloid, this out-phase interface helps to improve ionic polymer/Al
2O
3The ionic conductivity of composite package.
Fig. 2 is ionic polymer/Al
2O
3Lithium cell the 5th of composite package and the 100th charging and discharging curve, carried out 100 charge and discharge cycles after, its capability retention is 98% of an initial capacity, presents the excellent charging and discharging cycle performance.
Fig. 3 is the ionic polymer/Al of embodiment 6 preparations
2O
3The ESEM picture of composite package, picture can show composite package behind the electrolyte solution dipping, still are made up of the microtexture of its film colloidal particle and ceramic packing particle.
Claims (14)
1. ionic polymer/ceramic packing composite film material is characterized in that: it is to be made up of with the ceramic packing particle that is dispersed in wherein the acrylic polymer colloidal particle that the surface has a sulfonate groups.
2. according to claims 1 described ionic polymer/ceramic packing composite film material; It is characterized in that: said polymeric colloid particle is a methyl acrylate base polymer colloidal particle, and said ceramic packing particle is MOX or composite oxide of metal particle.
3. according to claims 2 described ionic polymer/ceramic packing composite film materials, it is characterized in that: ceramic packing particle shared mass percent in said composite film material is 10-60%, preferably 15-50%, more preferably 25-40%.
4. according to claims 2 described ionic polymer mould materials, it is characterized in that: said sulfonate groups is one or more in vinylsulfonate, allylsulfonate, methallylsulfonic acid salt, allyloxy hydroxypropyl sulphonate, hydroxyethyl methacrylate propyl sulfonic acid salt, 2-acrylamido-2-methyl propane sulfonic acid salt, the styrene sulfonate.
5. according to claims 1～3 each described ionic polymer/ceramic packing composite film material; It is characterized in that: in said ionic polymer/ceramic packing composite film material; The average particle size range of colloidal particle is 10nm～1.0 μ m, the average particle size range 10nm of ceramic packing particle～5.00 μ m; Preferably, the average particle size range of colloidal particle is 20～200nm, the average particle size range 20nm of ceramic packing particle～0.5 μ m; More preferably 20nm～200nm.
6. according to claims 4 described ionic polymer/ceramic packing composite film materials, it is characterized in that: the thickness of said ionic polymer/ceramic packing composite package is 10～40 μ m.
7. the preparation method of claims 1 described ionic polymer/ceramic packing composite film material; It is characterized in that: form in the process of polymeric colloid particle in polyreaction; Adding the response type sulfosalt surfactant is emulsifying agent, and synthetic surface has the acrylic polymer colloid emulsion of sulfonate groups, then; Add MOX or composite oxide of metal particle, film forming, drying both get after mixing.
8. according to the preparation method of claims 7 described ionic polymer/ceramic packing composite film materials, it is characterized in that: the response type sulfosalt surfactant is that one or more mixing in vinylsulfonate, allylsulfonate, methallylsulfonic acid salt, allyloxy hydroxypropyl sulphonate, hydroxyethyl methacrylate propyl sulfonic acid salt, 2-acrylamido-2-methyl propane sulfonic acid salt, the styrene sulfonate are used; Wherein, positively charged ion is lithium ion, sodium ion or potassium ion.
9. according to the preparation method of claims 7 described ionic polymer/ceramic packing composite film materials, it is characterized in that: the process following steps:
Synthesizing of a, polymer latex precursor emulsion: colloid protective agent and zero(ppm) water are joined in the reaction flask; Heated and stirred is up to dissolving fully; Add response type sulfosalt surfactant, polymerization reaction monomer and linking agent and mix, add the initiator polyreaction then and obtain the polymer latex precursor emulsion;
The preparation of b, ceramic packing slurry: in zero(ppm) water, add ceramic packing and dispersion agent, after being uniformly dispersed, with ball mill dispersions of further milling, cross 200 purposes and sieve again;
C, with the ceramic packing slurry that adds step b preparation in the polymer latex precursor emulsion of step a, be coated in after being uniformly dispersed on the plastics base band, peel off after the drying, promptly get.
10. according to the preparation method of claims 9 described ionic polymer/ceramic packing composite film materials, it is characterized in that: said polymerization reaction monomer is a methyl acrylate.
11. the preparation method according to claims 10 described ionic polymer/ceramic packing composite film materials is characterized in that: also add second kind of polymerization single polymerization monomer CH in the polymerization reaction system
2=CR
1R
2Carry out polyreaction;
Wherein, R
1=-H or-CH
3
R
2=-C
6H
5,-OCOCH
3,-CN ,-C
4H
6ON ,-C
2H
3CO
3,-COO (CH
2)
nCH
3, n is 0～14, in any one or more mix to use.
12. the preparation method according to claims 9 described ionic polymer/ceramic packing composite film materials is characterized in that: said second kind of monomer consumption is 2～10% of polymerization single polymerization monomer gross weight.
13. preparation method according to each described ionic polymer/ceramic packing composite film material of claims 9-12; It is characterized in that: the said colloid protective agent of step 1 is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably Z 150PH; The consumption of colloid protective agent is 5～30% of a polymerization reaction monomer gross weight; Further preferred scheme is, said dispersion agent is a kind of in Z 150PH, polyoxyethylene, polyacrylate, the PVP K120, preferably polyethylene alcohol; In the said ceramic packing slurry, the content of ceramic packing is 80～95%, the content 5～20% of dispersion agent, and solid content of slurry is 20～50%.
14. lithium secondary battery is characterized in that: it is to be that barrier film or ionic polymer/ceramic packing composite film material of being prepared from each said method of claims 7-13 are barrier film with each described ionic polymer/ceramic packing composite film material of claims 1-6.
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| CN201210219590.8A CN102719046B (en) | 2012-06-28 | 2012-06-28 | Ionic polymer/ceramic composite membrane material, preparation method thereof and lithium secondary battery |
| TW102112014A TWI511352B (en) | 2012-06-04 | 2013-04-03 | Ion polymer film material and its preparation method and lithium secondary battery |
| PCT/CN2013/073856 WO2013181967A1 (en) | 2012-06-04 | 2013-04-08 | Ion polymer membrane material, preparation process therefor and lithium secondary battery |
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| EP3375797A1 (en) * | 2017-03-14 | 2018-09-19 | Karlsruher Institut für Technologie | Filler polyester, method for their preparation and their use |
| CN107170944A (en) * | 2017-05-17 | 2017-09-15 | 贵州理工学院 | Self-supporting polymeric film material for lithium rechargeable battery and preparation method thereof |
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| CN112952203A (en) * | 2021-02-26 | 2021-06-11 | 大连交通大学 | Intelligent lithium-sulfur battery based on shape memory effect |
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