CN104151588B - Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries - Google Patents
Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries Download PDFInfo
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- CN104151588B CN104151588B CN201410333079.XA CN201410333079A CN104151588B CN 104151588 B CN104151588 B CN 104151588B CN 201410333079 A CN201410333079 A CN 201410333079A CN 104151588 B CN104151588 B CN 104151588B
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- lithium
- sulfide
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- barrier film
- sulfur cell
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 41
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 26
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 3
- 229910052744 lithium Inorganic materials 0.000 claims description 41
- 229920000557 Nafion® Polymers 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 39
- 230000004888 barrier function Effects 0.000 claims description 39
- -1 polyethylene Polymers 0.000 claims description 37
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 23
- 229920001155 polypropylene Polymers 0.000 claims description 23
- 229920001021 polysulfide Polymers 0.000 claims description 23
- 239000005077 polysulfide Substances 0.000 claims description 23
- 150000008117 polysulfides Polymers 0.000 claims description 23
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 22
- 150000004862 dioxolanes Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 9
- 239000005083 Zinc sulfide Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003014 ion exchange membrane Substances 0.000 abstract 3
- 239000010408 film Substances 0.000 description 66
- 210000004027 cell Anatomy 0.000 description 38
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 14
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 7
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium-sulfur batteries, and aims to provide a diaphragm for lithium-sulfur batteries and a preparation method of lithium-sulfur batteries. The preparation method of the diaphragm for lithium-sulfur batteries comprises the following steps: respectively preparing a polyolefin fiber reinforced lithium ion exchange membrane containing metal sulfide and a poly-lithium sulfide solution, and mixing the polyolefin fiber reinforced lithium ion exchange membrane containing metal sulfide and the poly-lithium sulfide solution so as to obtain a metal sulfide containing & poly-lithium sulfide doped & polyolefin fiber reinforced diaphragm for lithium-ion batteries; and a lithium-sulfur battery comprises electrolyte, a cathode, an anode and the prepared diaphragm for lithium-sulfur batteries. The metal sulfide containing & polyolefin fiber reinforced lithium ion exchange membrane prepared according to the invention has an extremely low internal resistance, good chemical stability and thermal stability and excellent cycle characteristic; and the diaphragm is simple in manufacturing process and pollution-free, and high in safety and high reliability.
Description
Technical field
The present invention is with regard to lithium-sulfur cell technical field, particularly to the system of a kind of lithium-sulfur cell barrier film and its lithium-sulfur cell
Preparation Method.
Background technology
Lithium-sulfur cell is one kind of lithium ion battery, using element sulphur as the positive electrode of battery, has lightweight, capacity
Greatly, the advantages of memory-less effect.The specific energy of lithium-sulfur cell is far above commercial wide variety of lithium ion battery.And, sulphur
It is a kind of environmental friendliness element, environment is not polluted substantially.Lithium-sulfur cell is the very promising lithium ion battery of one kind.
With lithium metal as negative material, using liquid electrolyte, during electric discharge, negative reaction loses electronics for lithium to lithium-sulfur cell
It is changed into lithium ion, positive pole reacts and generates sulfide for sulphur with lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is
The discharge voltage being provided by lithium-sulfur cell.Under applied voltage effect, the positive pole of lithium-sulfur cell and negative reaction are inversely carried out,
It is charging process.Elemental sulfur according to unit mass is changed into S completely2-The electricity that can be provided by can draw the theoretical discharge matter of sulphur
Amount specific capacity is 1675mAh g-1, the theoretical discharge specific discharge capacity of elemental lithium is 3860mAh g-1.The theory of lithium-sulfur cell is put
Piezoelectric voltage is 2.287V, and sulphur and lithium react generation lithium sulfide (Li completely2When S), the theoretical discharge mass ratio of corresponding lithium-sulfur cell
Energy is 2600Wh kg-1.
The charging and discharging reaction of sulfur electrode is more complicated, the intermediate product that sulfur electrode is produced in charging and discharging reaction
Also clearly do not recognize.The discharge process of sulfur electrode mainly includes two steps, corresponds to two discharge platforms respectively：(1) right
Answer S8Circulus be changed into Sn 2-The chain structure of (3≤n≤7) ion, and and Li+In conjunction with the poly- lithium sulfide (Li of generation2Sn), should
Discharge platform near reaction corresponding 2.4～2.1V on discharge curve；(2) corresponding Sn 2-The chain structure of ion is changed into S2-With
S2 2-And and Li+In conjunction with generation Li2S2And Li2S, longer discharge platform near 2.1～1.8V in the corresponding discharge curve of this reaction,
This platform is the main discharge region of lithium-sulfur cell.It is located at the corresponding elemental sulfur of 2.5～2.05V potential region upon discharging also primary
Become the reduction further of solvable polysulfide and polysulfide, positioned at many sulfurations that 2.05～1.5V potential region correspondence is solvable
Thing reduction generates lithium sulfide solid film, and it covers in conductive carbon matrix surface.During charging, Li in sulfur electrode2S and Li2S2Oxidized
S8And Sm 2-(6≤m≤7), can not be completely oxidized to S8, near this charging reaction corresponding 2.5～2.4V in charging curve
Charging platform.The maximum problem of lithium-sulfur cell is at present：Form the poly- lithium sulfide being dissolved in electrolyte, dissolving in charge and discharge process
Poly- lithium sulfide react with negative metal lithium, cause capacitance loss, lead to lithium-sulfur cell capacity fast decay, show extreme difference
Cycle life.
Traditional lithium ion battery separator mostly is the polyolefin porous membrane of high-strength thin-film, has electronic isolation, protects
The mechanical isolation of card both positive and negative polarity；Have certain aperture and porosity it is ensured that low resistance and high ionic conductivity (lithium ion has
Permeability well)；Electrolyte resistance corrodes (possessing chemistry and electrochemical stability)；Electrolyte wellability is good and high imbibition energy
Power；Enough mechanical properties (puncture strength, tensile strength etc.).Representative barrier film has Kynoar (PVDF), polyethylene, gathers
Propylene microcellular film, its ionic conductivity depends on aperture and the porosity of film.Produce in lithium-sulfur cell charge and discharge process
Polysulfide ion can readily pass through barrier film, reacts with the lithium metal of negative pole, consumes just very effective active material：Sulphur, thus cause lithium
The drastically decline of sulphur battery capacity, shows the battery cycle life of extreme difference.
Amberplex is a kind of macromolecule having containing ionic group, to the ion in solution and selecting through ability
Film.Because general mainly use its ion-selective permeability, also referred to as ion-selective permeability film in application.From
Proton exchange needs larger exchange capacity (ion-selective permeability is good, and conductive capability is strong), suitable imbibition ability, electric conductivity
Height, selective penetrated property is good, has higher mechanical strength and chemically and thermally stability.Representative amberplex has proton to hand over
Change film, such as perfluorinated sulfonic resin film, it is commonly called as Nafion membrane, it is a kind of most widely used in Proton Exchange Membrane Fuel Cells
Amberplex.Nafion membrane through ion exchange, by Li+Substitute the proton in Nafion membrane, can get Li+Type Nafion
Film, for lithium-sulfur cell as barrier film [Energy Environ.Sci., 7 (2014) 347-353.].But Li+Type Nafion
In film, lithium concentration is limited, also can adsorb polysulfide ion, cause the loss of positive electrode active material, lead to inducing capacity fading.And Li+
Type Nafion membrane intensity is weaker to form dendrite it is impossible to resist on lithium electrode, causes short circuit to cause barrier film to penetrate.In addition, Li+Type
Nafion membrane electrolyte absorbability is poor, embodies higher internal resistance, is unfavorable for high current charge-discharge.
Content of the invention
Present invention is primarily targeted at overcoming deficiency of the prior art, providing one kind with nano metal sulphide, gathering
Olefin(e) fibre, Li+Type perfluorinated sulfonic resin (Li+- Nafion) and polyvinylpyrrolidone (PVP) prepare for raw material, Jing Guoju
The heterogeneous membrane preparation method of sulfuration lithium doping and the lithium-sulfur cell using its preparation.For solving above-mentioned technical problem, the present invention
Solution be：
A kind of preparation method of lithium-sulfur cell barrier film is provided, specifically includes following step：
(1) take 100mL 1-METHYLPYRROLIDONE (NMP), add 3～10g Li+- Nafion resin and 3～10g PVP
After resin agitating dissolving, add 1g polyolefine fiber, after ultrasonic vibration (supersonic frequency 40kHz) disperses 30 minutes, add 0.5
～5g nano metal sulphide, after ultrasonic vibration (supersonic frequency 40kHz) disperses 2 hours, pouring film applicator into and being heated to 90 DEG C makes
NMP slow evaporation, obtains the enhanced lithium ion exchanged of polyolefine fiber containing metal sulfide after continuing 90 DEG C of heating 20 hours
Film；
(2) in the glove box of argon gas protection, add dioxolanes into reactor (reactors of 316 stainless steels)
(C3H6O2) and EGME obtain mixture, add 2.3g lithium sulfide, 10.3g elemental sulfur, add stirrer sealing reaction
After kettle, reactor removal glove box is placed on temperature control magnetic stirrer, stirring reaction 2～5h at 80 DEG C, then will be anti-
Move in glove box after answering kettle to be down to 10～30 DEG C, open the product that closure takes out in reactor, product is entered
Row obtains poly- lithium sulfide solution after filtering；
Wherein, the mixture containing dioxolanes and EGME is 100mL, and dioxolanes and EGME
Volume ratio is 1:1；
(3) in argon gas gloves for protection case, take the lithium proton-exchange-membrane being obtained in 1g step (1), be added to 50mL step
(2) in the poly- lithium sulfide solution being obtained in, impregnate 12h at 50 DEG C, that is, obtain polysulfide lithium doping, gathering containing metal sulfide
The enhanced lithium ion battery separator of olefin(e) fibre.
Improve as further, Li in described step (1)+The preparation method of-Nafion resin is：Take 100mL
Nafion solution (20wt% originates from E.I.Du Pont Company), adds 10g LiOH, and after stirring 30 minutes, surplus is fallen in centrifugation
LiOH, obtains Li+- Nafion solution, obtains Li after spray drying+- Nafion toner.
Improve as further, in described step (1), the preparation method of polyolefine fiber is：Take polyolefinic raw materials, melt
Carry out spinneret (traditional spinning process of textile industry) after melting to process, that is, obtain polyolefine fiber.
Improve as further, described polyolefinic raw materials adopt polyethylene or polypropylene.
Improve as further, the metallic element in described nano metal sulphide adopts copper, zinc or tin, its correspondence
Nano metal sulphide be nano-copper sulfide, nano-zinc sulfide and nanometer tin sulfide.
Improve as further, the synthesis technique of described nano-copper sulfide refers to：0.1 molar nitric acid copper is added to and contains
In the reactor of 100mL deionized water, add stirrer, after stirring and dissolving, add 2g PVP stirring and dissolving, by copper nitrate and sulphur
Change the mol ratio 1: 1 of sodium, weigh 0.1 mole of vulcanized sodium and add reactor, stirring reaction obtains nano-copper sulfide, mistake in 30 minutes
Filter, is dried after deionized water rinsing, obtains nano-copper sulfide powder；
Wherein, substitute above-mentioned copper nitrate respectively with the zinc nitrate and nitric acid tin of equimolar amounts, after above-mentioned steps operation,
Respectively obtain nano-zinc sulfide and nanometer tin sulfide powder.
Lithium-sulfur cell based on a kind of described lithium-sulfur cell barrier film is provided, including barrier film, positive pole, negative pole and electrolyte,
Described barrier film adopt polysulfide lithium doping, containing metal sulfide the enhanced lithium ion battery separator of polyolefine fiber, positive pole and
Negative pole is separately positioned on barrier film both sides and forms sandwich structure, and makes the electrode material side of positive pole and negative pole towards barrier film, is electrolysed
Liquid is built in sandwich structure；
Described electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and EGME
Mixture is solvent, and the volume ratio of dioxolanes and EGME is 1：1 mole of LiTFSI is contained in 1,1 liter of electrolyte.
Improve as further, described negative pole adopts metal lithium sheet.
Improve as further, the preparation method of described positive pole is：Take positive electrode, acetylene black and Li+- Nafion sets
After cosmetics end ground and mixed is uniform, adds the 1-METHYLPYRROLIDONE (NMP) as dispersant, be modulated into pasty state and be coated to aluminium film
Go up and dry in the shade, then in 100Kg cm-2Pressure under, will be compressing for the aluminium film after drying in the shade, that is, obtain positive pole；
Wherein, positive electrode, acetylene black, Li+The mass ratio 95: 5: 5 of-Nafion resin.
Improve as further, the preparation method of described positive electrode is：Take elemental sulfur and material with carbon element (commercially available Cabot
The BP2000 that company produces) after ground and mixed, it is placed in reactor (reactors of 316 stainless steels), reactor is taken out very
It is heated to 60 DEG C after sky, after reacting 5 hours, that is, positive electrode is obtained；
Wherein, elemental sulfur and the mass ratio of material with carbon element are 1: 2.
The operation principle of the present invention：
In step (1), in the presence of surfactant PVP, it is anti-that sulphophile element nitrate and vulcanized sodium pass through hydro-thermal method
Nanometer sulfide should be obtained.
Prepare amberplex and add PVP resin, make Li+- Nafion can more firmly with polyolefine fiber and receiving
Rice metal sulfide is combined together, and improves film strength；In film, the humidification of polyolefine fiber, improves film strength,
Effectively prevent lithium-sulfur cell process from penetrating, because barrier film caused by dendrite is formed on negative pole, the short circuit causing.
In lithium proton-exchange-membrane dipping process in poly- lithium sulfide solution, the nanometer sulfide in film absorbs substantial amounts of polysulfide
Change lithium to be fixed, improve lithium ion content in film, be conducive to improving the ionic conductivity of film；Meanwhile, in the electricity near film
Solution liquid sets up reverse polysulfide ion concentration gradient, hinders the polysulfide ion in positive pole to membrane diffusion, and Li+- Nafion has
Stop the effect that penetrates of polysulfide ion, greatly inhibit the polysulfide ion producing in lithium-sulfur cell charge and discharge process penetrate every
Film.
Compared with prior art, the invention has the beneficial effects as follows：
The present invention increased the ability of fixing polysulfide ion by dopen Nano metal sulfide in barrier film, lowers lithium sulphur electricity
The internal driving in pond；Through fiber reinforcement and interpolation PVP, improve the mechanical strength of barrier film；Modified by poly- lithium sulfide, improve
Amount in barrier film for the poly- lithium sulfide, greatly inhibits polysulfide ion to penetrate barrier film, eliminates polysulfide in charge and discharge process
Change the possibility that lithium is reacted with negative material, be conducive to stablizing of battery performance.
The enhanced lithium proton-exchange-membrane of the polyolefine fiber containing metal sulfide that the present invention prepares, has：(1) very
Low internal resistance；(2) good chemical stability and heat endurance；(3) excellent cycle characteristics；(4) barrier film manufacturing process is simple,
Pollution-free；(5) safety and reliability is high.
Brief description
Fig. 1 is the cycle life ratio of lithium-sulfur cell in embodiment 11 and the lithium-sulfur cell being obtained using conventional polypropylene barrier film
Relatively scheme.
Specific embodiment
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings：
A kind of preparation method of lithium-sulfur cell barrier film, specifically includes following step：
(1) take 100mL 1-METHYLPYRROLIDONE (NMP), add 3～10g Li+- Nafion resin and 3～10g PVP
After resin agitating dissolving, add 1g polyolefine fiber, after ultrasonic vibration (supersonic frequency 40kHz) disperses 30 minutes, add 0.5
～5g nano metal sulphide, after ultrasonic vibration (supersonic frequency 40kHz) disperses 2 hours, pouring film applicator into and being heated to 90 DEG C makes
NMP slow evaporation, obtains the enhanced lithium ion exchanged of polyolefine fiber containing metal sulfide after continuing 90 DEG C of heating 20 hours
Film；
Wherein, Li+The preparation method of-Nafion resin is：(20wt% originates from Du Pont public to take 100mL Nafion solution
Department), add 10g LiOH, after stirring 30 minutes, the LiOH of surplus is fallen in centrifugation, obtains Li+- Nafion solution, spraying is dry
Li is obtained after dry+- Nafion toner.The preparation method of polyolefine fiber is：Take polyolefinic raw materials, sprayed after melting
Silk (traditional spinning process of textile industry) is processed, that is, obtain polyolefine fiber；Polyolefinic raw materials adopt polyethylene or polypropylene.
Metallic element in nano metal sulphide adopts copper, zinc and tin.
Wherein, nano-copper sulfide is obtained by synthesis technique once：Copper nitrate (0.1 mole) is added to and goes containing 100mL
In the reactor of ionized water, add stirrer, after stirring and dissolving, add 2g PVP stirring and dissolving, by copper nitrate and vulcanized sodium
Mol ratio 1: 1 weighs (0.1 mole) of vulcanized sodium addition reactor, and stirring reaction obtains nano-copper sulfide in 30 minutes, filters, go from
It is dried after sub- water rinsing, obtain nano-copper sulfide powder.
Wherein, substitute above-mentioned copper nitrate respectively with the zinc nitrate and nitric acid tin of equimolar amounts, after above-mentioned steps operation,
Respectively obtain nano-zinc sulfide and nanometer tin sulfide powder.
(2) in the glove box of argon gas protection, add dioxolanes (C into the reactor of 316 stainless steels3H6O2)
Obtain 100mL mixture with EGME, the volume ratio of dioxolanes and EGME is 1:1, add 2.3g sulfuration
Lithium, 10.3g elemental sulfur, after adding stirrer sealed reactor, reactor removal glove box are placed in temperature control magnetic stirrer
On, stirring reaction 2～5h at 80 DEG C, then reactor is down to after 10～30 DEG C and moves in glove box, open closure and take
Go out the product in reactor, after product is filtered, obtain poly- lithium sulfide solution；
(3) in argon gas gloves for protection case, take the lithium proton-exchange-membrane being obtained in 1g step (1), be added to 50mL step
(2) in the poly- lithium sulfide solution being obtained in, impregnate 12h at 50 DEG C, that is, obtain polysulfide lithium doping, gathering containing metal sulfide
The enhanced lithium ion battery separator of olefin(e) fibre.
There is provided based on a kind of described lithium-sulfur cell of lithium-sulfur cell barrier film, including barrier film, positive pole, negative pole and electrolyte, institute
State barrier film and adopt polysulfide lithium doping, the enhanced lithium ion battery separator of polyolefine fiber containing metal sulfide, positive pole and negative
Pole is separately positioned on barrier film both sides and forms sandwich structure, and makes the electrode material side of positive pole and negative pole towards barrier film, electrolyte
It is built in sandwich structure；
Described electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and EGME
Mixture is solvent, and the volume ratio of dioxolanes and EGME is 1：1 mole of LiTFSI is contained in 1,1 liter of electrolyte.
Described negative pole adopts metal lithium sheet.
The preparation method of described positive pole is：Take positive electrode, acetylene black and Li+- Nafion toner is with mass ratio 95:
After 5: 5 mixed grindings are uniform, add the 1-METHYLPYRROLIDONE (NMP) as dispersant, be modulated into pasty state and be coated in aluminium film
And dry in the shade, then in 100Kg cm-2Pressure under, will be compressing for the aluminium film after drying in the shade, that is, obtain positive pole.Wherein, positive pole material
Material preparation method be：After taking the elemental sulfur that mass ratio is 1: 2 and material with carbon element ground and mixed, it is placed in the anti-of 316 stainless steels
Answer in device, after reactor is vacuumized, be heated to 60 DEG C, after reacting 5 hours, that is, positive electrode is obtained.Wherein material with carbon element is commercially available
The BP2000 that Cabot Co., Ltd produces.
The following examples can make this professional professional and technical personnel that the present invention is more fully understood, but not with any side
Formula limits the present invention.
Prepared by embodiment 1 nano metal sulphide
Weigh copper nitrate (0.1 mole) to be added in the reactor containing 100mL deionized water, add stirrer, stirring is molten
Xie Hou, adds 2g PVP stirring and dissolving, weighs (0.1 mole) of vulcanized sodium by the mol ratio 1: 1 of copper nitrate and vulcanized sodium and adds instead
Answer kettle, stirring reaction obtains nano-copper sulfide in 30 minutes, filter, be dried after deionized water rinsing, obtain nano-copper sulfide powder.
Substitute above-mentioned copper nitrate with the zinc nitrate and nitric acid tin of equimolar amounts respectively, after above-mentioned steps operation, respectively
Obtain nano-zinc sulfide and nanometer tin sulfide powder.
Embodiment 2 Li+Prepared by-Nafion powder
10g LiOH is added, after stirring 30 minutes, surplus is fallen in centrifugation in Nafion solution (20wt%) 100mL
LiOH, obtains Li+- Nafion solution, obtains Li after spray drying+- Nafion toner.
Prepared by embodiment 3 polyolefine fiber
Polyethylene is heated to after 150 DEG C of meltings polyethylene fibre is obtained by spinneret machine spinneret.Polypropylene is heated to
After 190 DEG C of meltings, polypropylene fibre is obtained by spinneret machine spinneret.
The polypropylene fibre of embodiment 4 Containing Sulfur copper strengthens film preparation
Take 1-METHYLPYRROLIDONE (NMP) (100mL), add Li+- Nafion toner (3g) and PVP resin (3g)
After stirring and dissolving, the polypropylene fibre (1g) of 50 μm of the long 2cm diameter of addition, ultrasonic vibration (supersonic frequency 40kHz) disperses 30 points
Zhong Hou, after adding nano-copper sulfide (5g) ultrasonic vibration (supersonic frequency 40kHz) to disperse 2 hours, pours film applicator into and is heated to 90
DEG C make NMP slow evaporation, after continuing 90 DEG C of heating 20 hours, obtain the enhanced lithium ion exchanged of polypropylene fibre of Containing Sulfur copper
Film.
The polyethylene fibre of embodiment 5 Containing Sulfur zinc strengthens film preparation
Take 1-METHYLPYRROLIDONE (NMP) (100mL), add Li+- Nafion toner (10g) and PVP resin (5g)
After stirring and dissolving, the polyethylene fibre (1g) of 50 μm of the long 1cm diameter of addition, ultrasonic vibration (supersonic frequency 40kHz) disperses 30 points
Zhong Hou, after adding nano-zinc sulfide (2.5g) ultrasonic vibration (supersonic frequency 40kHz) to disperse 2 hours, pours film applicator into and is heated to
90 DEG C make NMP slow evaporation, and the enhanced lithium ion of polyethylene fibre obtaining Containing Sulfur zinc after continuing 90 DEG C of heating 20 hours is handed over
Change film.
The polypropylene fibre of embodiment 6 Containing Sulfur tin strengthens film preparation
Take 1-METHYLPYRROLIDONE (NMP) (100mL), add Li+- Nafion toner (5g) and PVP resin (10g)
After stirring and dissolving, the polypropylene fibre (1g) of 50 μm of the long 0.5cm diameter of addition, ultrasonic vibration (supersonic frequency 40kHz) dispersion 30
After minute, after adding nanometer tin sulfide (0.5g) ultrasonic vibration (supersonic frequency 40kHz) to disperse 2 hours, pour film applicator heating into
Make NMP slow evaporation to 90 DEG C, after continuing 90 DEG C of heating 20 hours, obtain the enhanced lithium ion of polypropylene fibre of Containing Sulfur tin
Exchange membrane.
Prepared by the poly- lithium sulfide solution of embodiment 7
In argon gas gloves for protection case, containing dioxolanes (C3H6O2) and EGME mixed thing (dioxolanes and
The volume ratio of EGME is 1:1) add lithium sulfide 2.3g, elemental sulfur 10.3g in the reactor of 100mL, add stirrer
Remove glove box after sealing, be placed on temperature control magnetic stirrer, stirring reaction 2h at 80 DEG C, after being down to 10 DEG C, move to glove box,
Open closure, be filtrated to get poly- lithium sulfide solution.
The poly- lithium sulfide that the polyethylene fibre of embodiment 8 Containing Sulfur copper strengthens film is processed
Polyethylene is heated to after 150 DEG C of meltings long 50 μm of polypropylene fibres of 3cm diameter are obtained by spinneret machine spinneret.
Take 1-METHYLPYRROLIDONE (NMP) (100mL), add Li+- Nafion toner (5g) and PVP resin (5g)
After stirring and dissolving, add above-mentioned polyethylene fibre (1g), after ultrasonic vibration (supersonic frequency 40kHz) disperses 30 minutes, add real
Apply in example 1 preparation nano-copper sulfide (1.5g) ultrasonic vibration disperse 2 hours after, pouring film applicator into and being heated to 90 DEG C makes NMP delay
The slow enhanced lithium proton-exchange-membrane of polyethylene fibre evaporating, obtaining Containing Sulfur copper after continuing 90 DEG C of heating 20 hours.
In argon gas gloves for protection case, containing dioxolanes (C3H6O2) and EGME mixture (dioxolanes
Volume ratio with EGME is 1:1) add lithium sulfide 2.3g, elemental sulfur 10.3g in the reactor of 100mL, add stirring
Remove glove box after son sealing, be placed on temperature control magnetic stirrer, stirring reaction 3.5h at 80 DEG C, after being down to 20 DEG C, move to gloves
Case, opens closure, is filtrated to get poly- lithium sulfide solution.
By the polyethylene fibre enhanced lithium proton-exchange-membrane 1g of above-mentioned Containing Sulfur copper, add above-mentioned poly- lithium sulfide solution
In 50mL, at 50 DEG C dipping 12h obtain polysulfide lithium doping, Containing Sulfur copper the enhanced lithium ion battery of polyethylene fibre every
Film.
Prepared by embodiment 9 positive electrode
It is placed in elemental sulfur and material with carbon element in mass ratio 1: 2 ground and mixed in the reactor of 316 stainless steels, take out true
It is heated to 60 DEG C after sky, after 5 hours, obtain positive electrode.
Prepared by embodiment 10 positive pole
Positive electrode and Li in acetylene black and embodiment two in mass ratio 95: 5: 5 Example 9+- Nafion resin-oatmeal
After last ground and mixed is uniform, adds the 1-METHYLPYRROLIDONE (NMP) as dispersant, be modulated into pasty state and be coated in aluminium film simultaneously
Dry in the shade, then in 100Kg cm-2Pressure under compressing, obtain positive pole.
Prepared by embodiment 11 lithium-sulfur cell
Polypropylene is heated to after 150 DEG C of meltings long 50 μm of polypropylene fibres of 2cm diameter are obtained by spinneret machine spinneret.
Take 1-METHYLPYRROLIDONE (NMP) (100mL), add Li+- Nafion toner (5g) and PVP resin (5g)
After stirring and dissolving, add above-mentioned polypropylene fibre (1g), after ultrasonic vibration (supersonic frequency 40kHz) disperses 30 minutes, add real
Apply in example 1 preparation nano-zinc sulfide (1.5g) ultrasonic vibration disperse 2 hours after, pouring film applicator into and being heated to 90 DEG C makes NMP delay
The slow enhanced lithium proton-exchange-membrane of polypropylene fibre evaporating, obtaining Containing Sulfur zinc after continuing 90 DEG C of heating 20 hours.
In argon gas gloves for protection case, containing dioxolanes (C3H6O2) and EGME mixture (dioxolanes
Volume ratio with EGME is 1:1) add lithium sulfide 2.3g, elemental sulfur 10.3g in the reactor of 100mL, add stirring
Remove glove box after son sealing, be placed on temperature control magnetic stirrer, stirring reaction 5h at 80 DEG C, after being down to 30 DEG C, move to gloves
Case, opens closure, is filtrated to get poly- lithium sulfide solution.
By the polypropylene fibre enhanced lithium proton-exchange-membrane 1g of above-mentioned Containing Sulfur zinc, add above-mentioned poly- lithium sulfide solution
In 50mL, at 50 DEG C dipping 12h obtain polysulfide lithium doping, Containing Sulfur zinc the enhanced lithium ion battery of polypropylene fibre every
Film.
The electrode material side of the positive pole that embodiment 10 is obtained and metal lithium sheet opposite with above-mentioned lithium ion battery separator shape
Become sandwich structure, built-in electrolyte；Electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and
The mixture of EGME is solvent, and the volume ratio of dioxolanes and EGME is 1：1, rub containing one in one liter of electrolyte
You are LiTFSI.
Fig. 1 is the cycle life ratio of lithium-sulfur cell in embodiment 11 and the lithium-sulfur cell being obtained using conventional polypropylene barrier film
Relatively scheme.The electricity that ordinate unit is discharged by every gram of sulphur.Charge-discharge magnification：0.2C, temperature：45℃.Curve 1 is to use polysulfide
The discharge capacity circulation changing the lithium-sulfur cell of polypropylene fibre enhancing lithium ion battery separator preparation of lithium doping, Containing Sulfur zinc is steady
Qualitative, curve 2 is the discharge capacity cyclical stability of the lithium-sulfur cell using traditional lithium battery polypropylene diaphragm preparation.Result table
Bright, be used polysulfide lithium doping, Containing Sulfur zinc polypropylene fibre strengthen lithium proton-exchange-membrane as lithium-sulfur cell barrier film, no
But effectively increase the cycle life of lithium-sulfur cell, also improve its initial capacity.Fact proved, polysulfide lithium doping, contain metal
The polyolefine fiber of sulfide strengthens lithium proton-exchange-membrane and is more suitable for lithium-sulfur cell than conventional membrane.
Finally it should be noted that listed above be only the present invention specific embodiment.It is clear that the invention is not restricted to
Above example, can also have many variations.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation going out or associating, are all considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium-sulfur cell barrier film is it is characterised in that specifically include following step：
(1) take 100mL 1-METHYLPYRROLIDONE (NMP), add 3～10g Li+- Nafion resin and 3～10g PVP resin stir
After mixing dissolving, add 1g polyolefine fiber, after ultrasonic vibration disperses 30 minutes, add 0.5～5g nano metal sulphide, surpass
After acoustic vibration disperses 2 hours, pouring film applicator into and being heated to 90 DEG C makes NMP slow evaporation, obtains after continuing 90 DEG C of heating 20 hours
The enhanced lithium proton-exchange-membrane of polyolefine fiber containing metal sulfide；
(2) in the glove box of argon gas protection, add dioxolanes (C into reactor3H6O2) and EGME mixed
Thing, adds 2.3g lithium sulfide, 10.3g elemental sulfur, after adding stirrer sealed reactor, reactor is removed glove box juxtaposition
On temperature control magnetic stirrer, then reactor is down to immigration glove box after 10～30 DEG C by stirring reaction 2～5h at 80 DEG C
Interior, open the product that closure takes out in reactor, after product is filtered, obtain poly- lithium sulfide solution；
Wherein, the mixture containing dioxolanes and EGME is 100mL, and the volume of dioxolanes and EGME
Than for 1:1；
(3) in argon gas gloves for protection case, take the lithium proton-exchange-membrane being obtained in 1g step (1), be added in 50mL step (2)
In prepared poly- lithium sulfide solution, impregnate 12h at 50 DEG C, that is, obtain polysulfide lithium doping, the polyolefin containing metal sulfide
Fibre-reinforced lithium ion battery separator.
2. a kind of preparation method of lithium-sulfur cell barrier film according to claim 1 is it is characterised in that in described step (1)
Li+The preparation method of-Nafion resin is：Take 100mL Nafion solution, add 10g LiOH, after stirring 30 minutes, centrifugation
Separate the LiOH of surplus, obtain Li+- Nafion solution, obtains Li after spray drying+- Nafion toner.
3. a kind of preparation method of lithium-sulfur cell barrier film according to claim 1 is it is characterised in that in described step (1)
The preparation method of polyolefine fiber is：Take polyolefinic raw materials, carry out spinneret process after melting, that is, obtain polyolefine fiber.
4. a kind of preparation method of lithium-sulfur cell barrier film according to claim 3 is it is characterised in that described polyolefinic raw materials
Using polyethylene or polypropylene.
5. a kind of preparation method of lithium-sulfur cell barrier film according to claim 1 is it is characterised in that described nano metal sulphur
Metallic element in compound adopts copper, zinc or tin, and its corresponding nano metal sulphide is nano-copper sulfide, nano-zinc sulfide
And nanometer tin sulfide.
6. a kind of preparation method of lithium-sulfur cell barrier film according to claim 5 is it is characterised in that described nano-copper sulfide
Synthesis technique refer to：0.1 molar nitric acid copper is added in the reactor containing 100mL deionized water, adds stirrer, stirring
After dissolving, add 2g PVP stirring and dissolving, by the mol ratio 1: 1 of copper nitrate and vulcanized sodium, weigh 0.1 mole of vulcanized sodium and add instead
Answer kettle, stirring reaction obtains nano-copper sulfide in 30 minutes, filter, be dried after deionized water rinsing, obtain nano-copper sulfide powder；
Wherein, substitute above-mentioned copper nitrate respectively with the zinc nitrate and nitric acid tin of equimolar amounts, after above-mentioned steps operation, respectively
Obtain nano-zinc sulfide and nanometer tin sulfide powder.
7. the lithium-sulfur cell based on a kind of lithium-sulfur cell barrier film described in claim 1, including barrier film, positive pole, negative pole and electrolysis
Liquid is it is characterised in that described barrier film adopts polysulfide lithium doping, the enhanced lithium-ion electric of polyolefine fiber containing metal sulfide
Pond barrier film, positive pole and negative pole are separately positioned on barrier film both sides and form sandwich structure, and make the electrode material side of positive pole and negative pole
Towards barrier film, electrolyte is built in sandwich structure；
Described electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and EGME mixing
Thing is solvent, and the volume ratio of dioxolanes and EGME is 1：1 mole of LiTFSI is contained in 1,1 liter of electrolyte.
8. lithium-sulfur cell according to claim 7 is it is characterised in that described negative pole adopts metal lithium sheet.
9. lithium-sulfur cell according to claim 7 is it is characterised in that the preparation method of described positive pole is：Take positive electrode,
Acetylene black and Li+After-Nafion toner ground and mixed is uniform, add the 1-METHYLPYRROLIDONE (NMP) as dispersant,
It is modulated into pasty state to be coated in aluminium film and dry in the shade, then in 100Kg cm-2Pressure under, will be compressing for the aluminium film after drying in the shade,
Obtain positive pole；
Wherein, positive electrode, acetylene black, Li+The mass ratio 95: 5: 5 of-Nafion resin.
10. lithium-sulfur cell according to claim 9 is it is characterised in that the preparation method of described positive electrode is：Take simple substance
After sulphur and material with carbon element ground and mixed, it is placed in reactor, after reactor is vacuumized, is heated to 60 DEG C, after reacting 5 hours, that is, make
Obtain positive electrode；
Wherein, elemental sulfur and the mass ratio of material with carbon element are 1: 2.
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| CN104577083B (en) * | 2015-01-20 | 2017-02-22 | 浙江大学 | Positive electrode sulfur-carrying material of lithium-sulfur battery and preparation method of lithium-sulfur battery |
| CN104592541B (en) * | 2015-01-20 | 2017-10-27 | 浙江大学 | Micropore polybenzimidazole membrane and modified polyphenyl and imidazoles are the lithium-sulfur cell of barrier film |
| WO2017139993A1 (en) * | 2016-02-21 | 2017-08-24 | 肖丽芳 | Method for preparing doped lithium sulfide composite coated with graphene/carbon and having core-shell structure |
| CN105576290B (en) * | 2016-03-02 | 2018-04-10 | 合肥国轩高科动力能源有限公司 | Preparation method of single-ion gel electrolyte capable of blocking polysulfide ion shuttle effect |
| CN106099067B (en) * | 2016-08-12 | 2019-02-12 | 深圳博磊达新能源科技有限公司 | A kind of aluminium ion positive electrode for battery material and aluminium ion battery |
| CN108682772A (en) * | 2018-03-23 | 2018-10-19 | 孙备宽 | A kind of lithium ion battery non-porous barrier production method |
| CN109244330B (en) * | 2018-09-26 | 2020-06-05 | 湖南烁普新材料有限公司 | Preparation method of high-performance polyolefin composite battery diaphragm and lithium-sulfur battery |
| CN110148696B (en) * | 2019-05-10 | 2020-07-21 | 浙江大学 | Diaphragm capable of preventing lithium dendrite and rechargeable lithium battery |
| CN110323464B (en) * | 2019-06-27 | 2022-07-19 | 渤海大学 | Potassium air battery comprising polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane |
| CN112909430A (en) * | 2019-12-03 | 2021-06-04 | 恒大新能源技术(深圳)有限公司 | Lithium ion battery diaphragm and preparation method thereof and lithium ion battery |
| CN111628166B (en) * | 2020-06-04 | 2021-09-28 | 合肥工业大学 | Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof |
| CN113097646B (en) * | 2021-04-09 | 2022-09-20 | 山东星能安新能源科技有限公司 | Preparation method of lithium-sulfur battery diaphragm |
| CN114420916B (en) * | 2022-01-24 | 2023-08-25 | 福州大学 | Positive electrode material of lithium-sulfur battery, and preparation method and application thereof |
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