CN106784522A - A kind of solid lithium ion battery battery diaphragm and preparation method thereof - Google Patents
A kind of solid lithium ion battery battery diaphragm and preparation method thereof Download PDFInfo
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- CN106784522A CN106784522A CN201610988814.XA CN201610988814A CN106784522A CN 106784522 A CN106784522 A CN 106784522A CN 201610988814 A CN201610988814 A CN 201610988814A CN 106784522 A CN106784522 A CN 106784522A
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- crosslinked
- polyimidazole
- polypropylene
- lithium ion
- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 50
- 239000004743 Polypropylene Substances 0.000 claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 150000008365 aromatic ketones Chemical class 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 150000002460 imidazoles Chemical group 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims 2
- 239000002608 ionic liquid Substances 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical group ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to lithium ion battery separator preparing technical field, and in particular to a kind of solid lithium ion battery battery diaphragm and preparation method thereof.The battery diaphragm is made by the steps and forms：UV-crosslinked, polyimidazole crosslinked polypropylene perforated membrane the anion of the ethanol solution, polyimidazole salt and polypropylene porous film of configuration ion liquid polymer and UV-crosslinked dose of aromatic ketone is combined, finally dry be obtained solid lithium ion battery battery every.The present invention enhances the combination property of ion liquid polymer by polypropylene porous film, prepared solid lithium ion battery battery diaphragm finished product preferably overcomes existing ionic liquid barrier film low intensity, difficult shaping, flimsy defect, with good strength and stability, certain application value is shown.
Description
Technical field
The invention belongs to lithium ion battery separator preparing technical field, and in particular to a kind of solid lithium ion battery battery
Barrier film and preparation method thereof.
Background technology
All-solid lithium-ion battery has the advantages that security performance is high, energy density is big, operating temperature is interval wide, be lithium from
The important directions of sub- battery development.In terms of security, inflammable and explosive organic electrolyte is to cause lithium ion battery to be asked safely
The key factor of topic, overcharges, the abnormal conditions such as internal short-circuit may cause liquid electrolyte to be generated heat, and have spontaneous combustion even to explode
Danger.And by the all-solid-state battery of organic electrolyte instead solid electrolyte, its security can be greatly improved.Additionally, right
For all-solid-state battery, due to that need not enclose liquid, battery exterior can simplify, so as to manufacture big face in volume to volume mode
Product unit, will be achieved the battery of big voltage cell.
The exploitation of solid electrolyte diaphragm is the prerequisite that all-solid lithium-ion battery realizes application.Study and recognized
For ionic liquid has the excellent specific properties such as electrochemical window is wide, heat endurance is good, fire retardant, before lithium cell electrolyte research
Along material (Chinese material is in progress, 2016,449).Simultaneously because ionic liquid has good ionic conductivity, thus preparing
The solid electrolyte barrier film of high conductivity can be formed after into gel or polymerization.And for solid electrolyte research, it is domestic
The more extensive solid electrolyte of outer research at present is mainly polymer dielectric, the lithium phosphorus of polyoxyethylene and its derivative objects system
The class of inorganic electrolyte three of oxygen nitrogen film electrolyte and glassy state sulfide systems.But on the whole, the electricity of solid electrolyte
Conductance relative liquid electrolyte is relatively low, is the key factor for restricting all-solid lithium-ion battery development.
In general, in the prior art on all-solid lithium-ion battery existing some preferable achievements in research, concrete example
Such as：
Patent CN201110442911.6 discloses a kind of method of micropore ionic liquid/gel polymer electrolyte fiber,
A certain amount of polymer, lithium salts, ionic liquid are dissolved in NMP, three screw rod banburying extruders are then imported simultaneously and is mixed to get altogether
Mixed thing, extrudes through melt-blown spinneret, forms ionic liquid/gel polymer electrolyte ultrafine micropore fiber；
Patent CN201410120810.0 discloses a kind of lithium ion battery polymer dielectric and preparation method thereof, by ion
Liquid coats to get up to form the molecule of the microcapsule-type with high-lithium ion electrical conductivity with lighium polymer is led, then is disperseed
In a solvent, lithium salts and matrix material are added, a kind of lithium battery polymer dielectric film are obtained by coagulation bath film-forming,
The polymer dielectric not only has very high ion conductivity, is not in the phenomenon of leakage during use；
Patent CN201110347022. discloses a kind of method for preparing ionic liquid gel electrolyte, by film forming polymer
It is added in the mixed solvent formed by solvent-nonsolvent, homogeneous solution film is obtained, white porosity film is obtained；It is prepared by immersion
Il electrolyte in, obtain solid electrolyte membrane, the electrochemical window of film is more than 5V, with preferable electrical property, but
It is not to be fixed in perforated membrane because ionic liquid directly soaks, electrolyte solution is lost in use；
Patent CN200810162187.X discloses a kind of preparation method of high strength ionic liquid gel, by monomer, initiator, friendship
Connection agent carries out polymerisation in adding ionic liquid, obtains high strength ionic liquid gel；High strength ionic liquid prepared by it coagulates
Glue, maximal compressed stress overcomes ionic liquid gel low intensity, frangible, processing and deformation nature to a certain extent up to 30MPa
The shortcomings of difference, but its intensity is still below existing battery diaphragm（More than 100MPa）.
It is based on the studies above, although can to a certain extent improve solid lithium ion battery performance or quality but just actual
For prepared by production, still it is necessary further to study the electrolyte and battery diaphragm of solid lithium ion battery, to steadily improve
With improve solid lithium ion battery quality, and improve its properties of product.
The content of the invention
Present invention aim at a kind of solid lithium ion battery battery diaphragm is provided, so as to be solid lithium ion battery
The lasting improvement of energy lays the foundation.
Details are as follows for the technical scheme that the application is taken.
A kind of solid lithium ion battery battery diaphragm, is made by the steps and forms：
（1）The ethanol solution of configuration ion liquid polymer and UV-crosslinked dose of aromatic ketone, specially：
By equimolar than UV-crosslinked dose of ion liquid polymer and aromatic ketone be well mixed after, add 2 ~ 10 times of mixture
The absolute ethyl alcohol of weight, and make the abundant solvent of mixture in ethanol；
The cation of the ion liquid polymer is polyimidazole salt, is specially gathered（N- methyl-vinyls）It is imidazoles chlorine, poly-（N-
Ethyl-vinyl）It is imidazoles chlorine, poly-（N- methyl-vinyls）Imidazoles bromine is poly-（N- ethyl-vinyls）Imidazoles bromine；
UV-crosslinked dose of the polyaromatic ketone is benzophenone or acetophenone；
（2）Polyimidazole salt is UV-crosslinked with polypropylene porous film, specially：
Polypropylene porous film is immersed into step（1）Middle UV-crosslinked dose configured of ion liquid polymer-aromatic ketone（Poly- miaow
Azoles salt-UV-crosslinked dose of aromatic ketone）Ethanol solution in, immersion 0.5 ~ 5min after take out, after wiping excess surface solution, put
60 ~ 90 DEG C of 1 ~ 5min of heat treatment in drying box, most afterwards through 100 ~ 500mJ/cm2Ultraviolet irradiation 5- ~ 30s, hands over polyimidazole salt
It is linked in polypropylene loose structure and obtains being crosslinked with the polypropylene porous membrane of polyimidazole；
The polypropylene porous film is porosity 40 ~ 50%, the simple tension polypropylene screen of 50 ~ 200nm of average pore size；
（3）The anion of polyimidazole crosslinked polypropylene perforated membrane is combined, specially：
By step（2）In it is prepared be crosslinked with polyimidazole porous polypropylene film immerse 10 ~ 30wt% anion lithium salts it is water-soluble
In liquid, taken out after 0.5 ~ 5min of immersion, 90 ~ 105 DEG C of 1 ~ 5min of drying, you can obtain solid lithium ion battery battery diaphragm；
The anion lithium salts is two (trimethyl fluoride sulfonyl) amine lithiums, lithium hexafluoro phosphate or LiBF4.
It has been recognised by the inventors that flexible battery barrier film has that certain ionic conductance is low, mechanicalness in existing solid lithium ion
The defect of energy difference, thus be necessary to be further improved.The present invention enhances ion liquid polymerization by polypropylene porous film
The combination property of thing, it is strong that prepared solid lithium ion battery battery diaphragm finished product preferably overcomes existing ionic liquid barrier film
Low, the difficult shaping of degree, flimsy defect, with good strength and stability, show certain application value.
Specific embodiment
Explanation is further explained to the application with reference to embodiment, before specific embodiment is introduced, to following realities
Partial material situation is briefly discussed below in applying example.
Preparing raw material：
The cation of ion liquid polymer is polyimidazole salt：It is poly-（N- methyl-vinyls）It is imidazoles chlorine, poly-（N- ethyl vinyls
Base）It is imidazoles chlorine, poly-（N- methyl-vinyls）Imidazoles bromine and poly-（N- ethyl-vinyls）Imidazoles bromine etc. is Zhangjiagang people from Chu green wood
Material Science and Technology Ltd. product；
UV-crosslinked dose of polyaromatic ketone, benzophenone and acetophenone, are Chemical Reagent Co., Ltd., Sinopharm Group's product；
Polypropylene porous film used in following embodiments, its porosity 40 ~ 50%, 50 ~ 200nm of average pore size are that Wuhan favour is new by force
Energy and material Science and Technology Ltd. product；
Anion lithium salts：Two (trimethyl fluoride sulfonyl) amine lithiums, lithium hexafluoro phosphate, are that Jiangsu Guotai Chaowei New Material Co., Ltd. produces
Product；Phosphorus LiBF4 is Shanghai Nuo Tai Chemical Co., Ltd.s product.
Embodiment 1
The present embodiment provides solid lithium ion battery battery diaphragm, is made by the steps and forms：
（1）The ethanol solution of configuration ion liquid polymer and UV-crosslinked dose of aromatic ketone, specially：
By equimolar than UV-crosslinked dose of ion liquid polymer and aromatic ketone be well mixed after, add 2 times of weights of mixture
The absolute ethyl alcohol of amount, and make the abundant solvent of mixture in ethanol；
The cation of the ion liquid polymer is polyimidazole salt, is specially gathered（N- methyl-vinyls）Imidazoles chlorine；
UV-crosslinked dose of the polyaromatic ketone is benzophenone；
（2）Polyimidazole salt is UV-crosslinked with polypropylene porous film, specially：
Polypropylene porous film is immersed into step（1）Middle UV-crosslinked dose configured of ion liquid polymer-aromatic ketone（Poly- miaow
Azoles salt-UV-crosslinked dose of aromatic ketone）Ethanol solution in, immersion 0.5min after take out, after wiping excess surface solution, be placed in
60 DEG C of heat treatment 1min in drying box, most afterwards through 100mJ/cm2Ultraviolet irradiation 5s, makes polyimidazole salt be linked to the porous knot of polypropylene
Obtain being crosslinked with the polypropylene porous membrane of polyimidazole in structure；
The polypropylene porous film is porosity 40%, the simple tension polypropylene screen of average pore size 50nm；
（3）The anion of polyimidazole crosslinked polypropylene perforated membrane is combined, specially：
By step（2）In it is prepared be crosslinked with polyimidazole porous polypropylene film immerse 10wt% anion Aqueous Lithium Salts
In, taken out after immersion 0.5min, 90 DEG C dry 1min, you can obtain solid lithium ion battery battery diaphragm；
The anion lithium salts is two (trimethyl fluoride sulfonyl) amine lithiums.
To prepared solid lithium ion battery battery diaphragm, using AutoLab302N type electrochemical workstations（Exchange
Impedance analysis method）Measurement electrical conductivity, as a result shows：5.6V, 25 DEG C of lithium ion conductivities are 2.6 × 10-4Scm-1；Using upper
Hai Hualong WDW type electronic universal testers test its mechanical performance, as a result for：Longitudinal fracture intensity is 158MPa, elastic modelling quantity
For 1365 MPa, elongation at break are that 186%, puncture strength is 427gf.
Embodiment 2
The present embodiment provides the preparation process of solid lithium ion battery battery diaphragm with embodiment 1, only adjustment member reaction
Parameter is as follows：
Step（1）In：Polyimidazole salt is poly-（N- ethyl-vinyls）Imidazoles chlorine, UV-crosslinked dose of polyaromatic ketone is acetophenone,
Absolute ethyl alcohol consumption is 10 times of mixture weight；
Step（2）In：Polypropylene porous film is porosity 50%, the simple tension polypropylene screen of average pore size 200nm, during immersion
Between be 5min, dried process parameter be 90 DEG C heat treatment 5min, 500mJ/cm2Ultraviolet irradiation 30s；
Step（3）In：Anion lithium salts is two (trimethyl fluoride sulfonyl) amine lithiums, and concentration is 30wt%, soaks 5min, and 105 DEG C are done
Dry 5min.
Prepared solid lithium ion battery is detected with battery diaphragm, using AutoLab302N type electrochemical operations
Stand（Ac resistance analysis method）Measurement electrical conductivity, as a result shows：5.5V, 25 DEG C of lithium ion conductivities are 3.2 × 10-4Scm-1；
Using Shanghai China dragon WDW type electronic universal tester test mechanical performances, as a result for：Longitudinal fracture intensity is 146MPa, elasticity
Modulus is 1278 MPa, elongation at break is that 175%, puncture strength is 423gf.
Embodiment 3
The present embodiment provides the preparation process of solid lithium ion battery battery diaphragm with embodiment 1, only adjustment member reaction
Parameter is as follows：
Step（1）In：Polyimidazole salt is poly-（N- methyl-vinyls）Imidazoles bromine, UV-crosslinked dose of polyaromatic ketone is hexichol first
Ketone, absolute ethyl alcohol consumption is 7 times of mixture weight；
Step（2）In：Polypropylene porous film is porosity 43%, the simple tension polypropylene screen of average pore size 110nm, during immersion
Between be 3min, dried process parameter be 80 DEG C heat treatment 2min, 310mJ/cm2Ultraviolet irradiation 10s；
Step（3）In：Anion lithium salts is lithium hexafluoro phosphate, and concentration is 20wt%, soaks 4min, and 100 DEG C dry 2min.
Prepared solid lithium ion battery is detected with battery diaphragm, using AutoLab302N type electrochemical operations
Stand（Ac resistance analysis method）Measurement electrical conductivity, as a result shows：5.3V, 25 DEG C of lithium ion conductivities are 1.8 × 10-4Scm-1,
Using Shanghai China dragon WDW type electronic universal tester test mechanical performances, as a result for：Longitudinal fracture intensity is 143MPa, elasticity
Modulus is 1254 MPa, elongation at break is that 171%, puncture strength is 412gf.
Embodiment 4
The present embodiment provides the preparation process of solid lithium ion battery battery diaphragm with embodiment 1, only adjustment member reaction
Parameter is as follows：
Step（1）In：Polyimidazole salt is poly-（N- ethyl-vinyls）Imidazoles bromine, UV-crosslinked dose of polyaromatic ketone is acetophenone,
Absolute ethyl alcohol consumption is 10 times of mixture weight；
Step（2）In：Polypropylene porous film is porosity 46%, the simple tension polypropylene screen of average pore size 172nm, during immersion
Between be 3min, dried process parameter be 90 DEG C heat treatment 5min, 250mJ/cm2Ultraviolet irradiation 15s；
Step（3）In：Anion lithium salts is LiBF4, and concentration is 15wt%, soaks 1.5min, and 100 DEG C dry 3.5min.
Prepared solid lithium ion battery is detected with battery diaphragm, using AutoLab302N type electrochemical operations
Stand（Ac resistance analysis method）Measurement electrical conductivity, as a result shows：5.4V, 25 DEG C of lithium ion conductivities are 1.2 × 10-4Scm-1,
Using Shanghai China dragon WDW type electronic universal tester test mechanical performances, as a result show：Longitudinal fracture intensity is 138MPa, bullet
Property modulus be 1186 MPa, elongation at break be 172%, puncture strength be 408gf.
Claims (3)
1. a kind of solid lithium ion battery battery diaphragm, it is characterised in that be made by the steps and form：
（1）The ethanol solution of configuration ion liquid polymer and UV-crosslinked dose of aromatic ketone, specially：
By equimolar than UV-crosslinked dose of ion liquid polymer and aromatic ketone be well mixed after, add 2 ~ 10 times of mixture
The absolute ethyl alcohol of weight, and mixture is completely dissolved in absolute ethyl alcohol；
The cation of the ion liquid polymer is polyimidazole salt, is specially gathered（N- methyl-vinyls）It is imidazoles chlorine, poly-（N-
Ethyl-vinyl）It is imidazoles chlorine, poly-（N- methyl-vinyls）Imidazoles bromine is poly-（N- ethyl-vinyls）Imidazoles bromine；
UV-crosslinked dose of the polyaromatic ketone is benzophenone or acetophenone；
（2）Polyimidazole salt is UV-crosslinked with polypropylene porous film, specially：
Polypropylene porous film is immersed into step（1）The second of middle UV-crosslinked dose configured of ion liquid polymer-aromatic ketone
In alcoholic solution, taken out after 0.5 ~ 5min of immersion, after wiping excess surface solution, be placed in drying box 60 ~ 90 DEG C of heat treatments 1 ~
5min, most afterwards through 100 ~ 500mJ/cm2Ultraviolet irradiation 5- ~ 30s, makes polyimidazole salt be handed in being linked to polypropylene loose structure
It is associated with the polypropylene porous membrane of polyimidazole；
（3）The anion of polyimidazole crosslinked polypropylene perforated membrane is combined, specially：
By step（2）In it is prepared be crosslinked with polyimidazole polypropylene porous membrane immerse 10 ~ 30wt% anion lithium salts it is water-soluble
In liquid, taken out after 0.5 ~ 5min of immersion, 90 ~ 105 DEG C of 1 ~ 5min of drying, you can obtain solid lithium ion battery battery diaphragm；
The anion lithium salts is two (trimethyl fluoride sulfonyl) amine lithiums, lithium hexafluoro phosphate or LiBF4.
2. solid lithium ion battery battery diaphragm as claimed in claim 1, it is characterised in that step（2）In, the polypropylene
Porous membrane is porosity 40 ~ 50%, the simple tension polypropylene screen of 50 ~ 200nm of average pore size.
3. the preparation method of solid lithium ion battery battery diaphragm described in claim 1, it is characterised in that including following step
Suddenly：
（1）The ethanol solution of configuration ion liquid polymer and UV-crosslinked dose of aromatic ketone, specially：
After UV-crosslinked dose of ion liquid polymer and aromatic ketone are well mixed, the anhydrous of 2 ~ 10 times of weight of mixture is added
Ethanol, and make the abundant solvent of mixture in ethanol；
The cation of the ion liquid polymer is polyimidazole salt, is specially gathered（N- methyl-vinyls）It is imidazoles chlorine, poly-（N-
Ethyl-vinyl）It is imidazoles chlorine, poly-（N- methyl-vinyls）Imidazoles bromine is poly-（N- ethyl-vinyls）Imidazoles bromine；
UV-crosslinked dose of the polyaromatic ketone is benzophenone or acetophenone；
（2）Polyimidazole salt is UV-crosslinked with polypropylene porous film, specially：
Polypropylene porous film is immersed into step（1）The second of middle UV-crosslinked dose configured of ion liquid polymer-aromatic ketone
In alcoholic solution, taken out after 0.5 ~ 5min of immersion, after wiping excess surface solution, be placed in drying box 60 ~ 90 DEG C of heat treatments 1 ~
5min, most afterwards through 100 ~ 500mJ/cm2Ultraviolet irradiation 5- ~ 30s, makes polyimidazole salt be handed in being linked to polypropylene loose structure
It is associated with the polypropylene porous membrane of polyimidazole；
（3）The anion of polyimidazole crosslinked polypropylene perforated membrane is combined, specially：
By step（2）In it is prepared be crosslinked with polyimidazole porous polypropylene film immerse 10 ~ 30wt% anion lithium salts it is water-soluble
In liquid, taken out after 0.5 ~ 5min of immersion, 90 ~ 105 DEG C of 1 ~ 5min of drying, you can obtain solid lithium ion battery battery diaphragm；
The anion lithium salts is two (trimethyl fluoride sulfonyl) amine lithiums, lithium hexafluoro phosphate or LiBF4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610988814.XA CN106784522B (en) | 2016-11-10 | 2016-11-10 | A kind of solid lithium ion battery battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610988814.XA CN106784522B (en) | 2016-11-10 | 2016-11-10 | A kind of solid lithium ion battery battery diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106784522A true CN106784522A (en) | 2017-05-31 |
| CN106784522B CN106784522B (en) | 2019-07-16 |
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Cited By (2)
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| CN108232085A (en) * | 2017-12-25 | 2018-06-29 | 佛山市东航光电科技股份有限公司 | Poly ion liquid coated bacteria cellulose membrane and preparation method thereof |
| CN111416087A (en) * | 2020-03-18 | 2020-07-14 | 江苏厚生新能源科技有限公司 | Preparation method of novel thermal radiation cross-linked semi-solid lithium battery diaphragm |
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| CN101271968A (en) * | 2008-05-16 | 2008-09-24 | 辽源市鸿图纸业有限公司 | Mercury-free diaphragm paper for laminated cell |
| CN101935398A (en) * | 2010-06-24 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | High-electric conductivity aromatic polymer ionic liquid diaphragm material and preparation method thereof |
| CN103146018A (en) * | 2013-02-08 | 2013-06-12 | 上海中科高等研究院 | Preparation method of large-rate discharge porous diaphragm material and application of material |
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| CN101210075A (en) * | 2006-12-26 | 2008-07-02 | 中国科学院兰州化学物理研究所 | Polymer thin film containing ion liquid and preparing method thereof |
| CN101271968A (en) * | 2008-05-16 | 2008-09-24 | 辽源市鸿图纸业有限公司 | Mercury-free diaphragm paper for laminated cell |
| CN101935398A (en) * | 2010-06-24 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | High-electric conductivity aromatic polymer ionic liquid diaphragm material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232085A (en) * | 2017-12-25 | 2018-06-29 | 佛山市东航光电科技股份有限公司 | Poly ion liquid coated bacteria cellulose membrane and preparation method thereof |
| CN108232085B (en) * | 2017-12-25 | 2022-03-01 | 上海恩捷新材料科技有限公司 | Polyion liquid coated bacterial cellulose membrane and preparation method thereof |
| CN111416087A (en) * | 2020-03-18 | 2020-07-14 | 江苏厚生新能源科技有限公司 | Preparation method of novel thermal radiation cross-linked semi-solid lithium battery diaphragm |
| CN111416087B (en) * | 2020-03-18 | 2022-02-15 | 江苏厚生新能源科技有限公司 | Heat radiation cross-linking semi-solid lithium battery diaphragm and preparation method thereof |
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| CN106784522B (en) | 2019-07-16 |
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