CN115377606A - High-performance chitosan/polyacrylonitrile diaphragm for multifunctional lithium-sulfur battery and preparation method and application thereof - Google Patents
High-performance chitosan/polyacrylonitrile diaphragm for multifunctional lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- CN115377606A CN115377606A CN202211012444.8A CN202211012444A CN115377606A CN 115377606 A CN115377606 A CN 115377606A CN 202211012444 A CN202211012444 A CN 202211012444A CN 115377606 A CN115377606 A CN 115377606A
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- polyacrylonitrile
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 49
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 239000002121 nanofiber Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910013553 LiNO Inorganic materials 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
- 239000000835 fiber Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 229910018091 Li 2 S Inorganic materials 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The invention relates to a high-performance chitosan/polyacrylonitrile diaphragm for a multifunctional lithium-sulfur battery and a preparation method and application thereof, wherein chitosan is ultrasonically dispersed in a polyacrylonitrile solution to form uniformly dispersed suspension; spinning the obtained suspension on the surface of an aluminum foil by using an electrostatic spinning technology to form an electrostatic spinning nanofiber membrane, and standing at room temperature to volatilize a solvent; heating to convert polyacrylonitrile into preoxidized polyacrylonitrile. The invention simultaneously solves the problems of lithium dendritic crystal generation and polysulfide shuttling in the battery cycle process, and the prepared chitosan/polyacrylonitrile diaphragm has excellent cycle stability and coulombic efficiency.
Description
Technical Field
The invention belongs to the technical field of lithium battery diaphragms, and particularly relates to a high-performance chitosan/polyacrylonitrile diaphragm for a multifunctional lithium-sulfur battery, and a preparation method and application thereof.
Background
Energy is the basis on which human beings rely for survival and is the most fundamental driving force for the development of the human world. Problems such as energy shortage and environmental pollution due to economic development are becoming more severe. The new renewable energy source, such as the utilization of hydroenergy, solar energy etc. gradual marketization of electric automobile etc., the rapid development of various portable equipment all needs high-efficient practical energy storage and transportation system, but to new and type "green" energy storage device, when cutting about its "green", can decide whether the key that whether it is fit for the industrialization and uses is whether it has important index such as high power density, high energy density. New power systems, particularly secondary batteries, are currently important "green" energy storage devices.
The energy density of the lithium ion battery which is already marketed is close to the theoretical energy density of the lithium ion battery, and the requirement of some emerging mobile devices on high energy density of electric energy cannot be well met. The lithium-sulfur battery is an energy storage system with a bright prospect, the theoretical specific energy can reach 2600 Wh/kg, the raw material acquisition cost is low, and the environment is friendly, so that the lithium-sulfur battery has a huge development space. However, lithium sulfur batteries have some serious problems in practical applications-one aspect is the "shuttle effect" of polysulfides, i.e., sulfur is reduced to soluble long-chain lithium polysulfides (Li) during charge and discharge reactions 2 S m M is not less than 4 and not more than 8), produced Li 2 S m Will dissolve in the electrolyte and subsequently migrate to form shuttles. In the shuttling process, li 2 S m Further disproportionation to produce insulating Li 2 S 2 And Li 2 S, causing loss of active materials, resulting in fading of battery capacity; on the other hand, the growth and generation of lithium dendrite are shown, the lithium dendrite grows to a certain degree and is separated from the negative electrode to enter the electrolyte to form 'dead lithium', thereby reducing the metal benefit of the negative electrodeThe rate of utilization, the generation and development of lithium dendrites seriously hamper the long cycle stability of the battery and the safety of the battery, etc. Therefore, there is an urgent need to develop a stable and safe high-performance lithium-sulfur battery separator to promote the efficient development of the lithium battery industry.
Disclosure of Invention
In order to solve the problems in the prior art and better meet the requirements of social development on stable and safe secondary rechargeable lithium batteries, the invention provides a high-performance chitosan/polyacrylonitrile diaphragm for a multifunctional lithium-sulfur battery, a preparation method and application thereof, and simultaneously solves the problems of generation of lithium dendrites and polysulfide shuttling in the battery cycle process, so that the diaphragm has excellent cycle stability and coulombic efficiency.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a preparation method of a high-performance chitosan/polyacrylonitrile diaphragm for a multifunctional lithium-sulfur battery comprises the following steps:
(1) Ultrasonically dispersing chitosan powder in a polyacrylonitrile solution to form uniformly dispersed suspension;
(2) Spinning the suspension on the surface of an aluminum foil by using an electrostatic spinning technology to form an electrostatic spinning nanofiber membrane, and standing at room temperature to volatilize the solvent to form a chitosan/polyacrylonitrile fiber membrane;
(3) Heating the chitosan/polyacrylonitrile fiber membrane to convert polyacrylonitrile into preoxidized polyacrylonitrile;
(4) And drying to obtain the required lithium-sulfur battery diaphragm.
In a preferred embodiment of the invention, in the step (1), polyacrylonitrile (PAN) is dissolved in N, N-Dimethylformamide (DMF) solution to obtain a uniformly dispersed solution, and then chitosan is ultrasonically dispersed in the solution for 1 to 12 hours, and is magnetically stirred at a constant temperature for 6 to 24 hours at room temperature to obtain a uniformly dispersed suspension.
In a preferred embodiment of the invention, in the step (1), the mass ratio of chitosan to polyacrylonitrile is 1 to 1.
In a preferred embodiment of the invention, in step (1), the mass concentration of the chitosan/polyacrylonitrile solution is 10 to 20wt%.
In a preferred embodiment of the present invention, in the step (2), a polyacrylonitrile fiber membrane containing chitosan is prepared by using an electrospinning technique and is attached to the surface of the aluminum foil, and the membrane thickness is 0.05-0.10mm.
In a preferred embodiment of the present invention, in the step (3), the heating treatment is pre-oxidation treatment in a muffle furnace at 120-350 ℃, the heating rate is 1-5 ℃/min, the holding time at 120-350 ℃ is 1-5 hours, and the temperature is naturally reduced to 20-50 ℃ after holding, so that the polyacrylonitrile nano-fiber is converted into partially oxidized PAN (oxy-PAN).
The invention also protects the high-performance chitosan/polyacrylonitrile diaphragm for the multifunctional lithium-sulfur battery prepared by the preparation method.
The invention also protects the high-performance chitosan/polyacrylonitrile diaphragm for the multifunctional lithium-sulfur battery to be used for preparing the multifunctional lithium-sulfur battery.
In a preferred embodiment of the invention, the diaphragm and the two lithium metal sheet negative electrodes are assembled into a button battery, or the diaphragm, the lithium metal sheet negative electrodes and the sulfur positive electrode sheet are assembled into a button battery.
In a preferred embodiment of the present invention, the method for preparing the sulfur positive electrode sheet comprises: mechanically mixing high-purity sublimed sulfur, conductive carbon black and a gelatin solution according to a mass ratio of 63.
In a preferred embodiment of the invention, the solvent of the battery electrolyte used is DOL/DME =1 (volume ratio) and comprises 1M LiTFSI and 0.4M LiNO 3 As a solute.
In a preferred embodiment of the invention, the standing time of the assembled button cell is 8-12 hours; wherein the current density of the lithium pair battery is 1mA/cm 2 Deposition/stripping under conditionsAnd (5) carrying out a charge-discharge cycle test on the lithium-sulfur battery under the condition of multiplying power of 0.5C.
Compared with the prior art, the invention has the following beneficial effects:
the main material chitosan used in the invention is natural biological macromolecule, and has good physical and chemical properties such as adsorptivity, ion selectivity, biodegradability and the like. The abundant polar functional groups of the chitosan and the oxygen-containing functional groups of the pre-oxidized polyacrylonitrile, and the three-dimensional structure of the electrostatic spinning membrane can efficiently capture polysulfide, adjust the deposition/stripping behavior of lithium, effectively avoid the growth of lithium dendrite in the battery cycle process, inhibit the shuttle effect, and improve the long cycle stability and safety of the lithium-sulfur battery.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a graph comparing the cycle performance of a lithium-on-battery cell composed of the separator prepared in example 1 of the present invention with that of a lithium-on-battery cell composed of a general separator;
FIG. 2 is a graph showing a comparison of specific discharge capacities of a lithium sulfur battery comprising the separator prepared in example 1 of the present invention and a lithium sulfur battery comprising a general separator;
fig. 3 is a graph comparing coulombic efficiencies of a lithium sulfur battery composed of the separator prepared in example 1 of the present invention and a lithium sulfur battery composed of a general separator.
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited thereto, and any changes or modifications made thereto should be construed as being within the scope of the present invention.
The battery separator used in the examples was a common commercial separator, celgard 2325.
Example 1
(1) Preparation of a Stable and safe separator
Accurately weighing 1.2g of Polyacrylonitrile (PAN) to dissolve in 8.5g of N, N-Dimethylformamide (DMF) solution, accurately weighing 0.3g of Chitosan (CS) to disperse in the solution, ultrasonically stirring for 12h at the constant temperature of 30 ℃, then spinning the solution into a nanofiber membrane (the membrane thickness is 0.06 mm) on an aluminum foil by using an electrostatic spinning machine, and using an electrostatic spinning technology in the step (2) to obtain the following specific parameters: a22-gauge needle is adopted, the receiving distance is 18cm, the spinning voltage is 16KV, the advancing speed is 0.1mm/min, the temperature is 30 ℃, the humidity is 50%, and the mixture is kept stand for 12 hours at room temperature.
And (2) carrying out preoxidation heating process treatment on the prepared nanofiber membrane in a muffle furnace, wherein the temperature range of the heating process is from room temperature to 230 ℃, the heating rate is 2 ℃/min, the heat preservation time at 230 ℃ is 2 hours, after heat preservation, the temperature is naturally reduced to 30 ℃, the material is taken out, and a cutting machine is utilized to cut the material into small wafers with the diameter of 19 mm.
(2) Preparation of lithium-pair battery and lithium-sulfur battery
Assembling the diaphragm and two common metal lithium sheet cathodes into a CR2025 type button battery in a glove box, wherein the electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was allowed to stand for 10 hours. Similarly, a conventional separator and two lithium metal sheets were assembled into a lithium-pair battery as a control.
Assembling the diaphragm, a common metal lithium sheet cathode and a sulfur positive sheet into a CR2025 type button battery in a glove box, wherein the electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was allowed to stand for 10 hours. Similarly, a lithium sulfur battery was assembled by using a common separator, a lithium metal plate and a sulfur positive electrode as a control.
(3) Electrochemical performance testing of lithium on batteries
The cycle performance test of the lithium-lithium battery is carried out on the charging and discharging equipment, and the test conditions are as follows: the charging and discharging current density is 1.0mA/cm 2 And the charge and discharge amount is 1.0mAh/cm 2 . The results of the two cycle performance tests are shown in FIG. 1. As can be seen from the data in the figure, lithium assembled by using the separator prepared by the invention has smaller polarization voltage and longer and more stable cycle period for the battery, and the method for preparing the separator and the obtained separator are effective.
(4) Electrochemical performance testing of lithium sulfur batteries
And (3) carrying out cycle performance test on the lithium-sulfur battery on charging and discharging equipment under the test condition of 0.5C. The results of the two cycle performance tests are shown in fig. 2. As can be seen from the data in the figure, the lithium-sulfur battery assembled by the diaphragm prepared by the invention has higher specific discharge capacity and more stable cycle efficiency, which indicates that the diaphragm preparation method and the diaphragm obtained by the method are feasible.
Example 2
(1) Preparation of a Stable and safe separator
Accurately weighing 1.0g of Polyacrylonitrile (PAN) to dissolve in 8.0g of N, N-Dimethylformamide (DMF) solution, accurately weighing 1.0g of Chitosan (CS) to disperse in the solution, ultrasonically stirring for 1h at the constant temperature of 30 ℃ for 6h, then spinning the solution into a nanofiber membrane (the membrane thickness is 0.10 mm) on an aluminum foil by using an electrostatic spinning machine, and using an electrostatic spinning technology in the step (2) to obtain the following specific parameters: a22-gauge needle is adopted, the receiving distance is 18cm, the spinning voltage is 16KV, the advancing speed is 0.1mm/min, the temperature is 30 ℃, the humidity is 50%, and the mixture is kept stand for 12 hours at room temperature.
And (2) carrying out preoxidation heating process treatment on the prepared nanofiber membrane in a muffle furnace, wherein the temperature range of the heating process is from room temperature to 350 ℃, the heating rate is 5 ℃/min, the heat preservation time at 350 ℃ is 1 hour, after heat preservation, the temperature is naturally reduced to 50 ℃, and the material is taken out and cut into small wafers with the diameter of 19mm by using a cutting machine.
(2) Preparation of lithium-pair battery and lithium-sulfur battery
Assembling the diaphragm and two common metal lithium sheet cathodes into a CR2025 type button battery in a glove box, wherein the electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was left to stand for 8 hours. Similarly, a lithium-pair battery was assembled with two lithium metal sheets and a common separator as a control.
The diaphragm, a common metal lithium sheet cathode and a sulfur positive sheet are assembled into a CR2025 type button battery in a glove box, and the electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was left to stand for 8 hours. Similarly, a lithium sulfur battery was assembled by using a common separator, a lithium metal plate and a sulfur positive electrode as a control.
(3) Electrochemical performance testing of lithium on batteries
The cycle performance test of the lithium-lithium battery is carried out on the charging and discharging equipment, and the test conditions are as follows: the charging and discharging current density is 1.0mA/cm 2 And the charge and discharge amount is 1.0mAh/cm 2 . Lithium assembled with the separator prepared by the invention has smaller polarization voltage and longer and more stable cycle period for batteries.
(4) Electrochemical performance testing of lithium sulfur batteries
And (3) carrying out cycle performance test on the lithium-sulfur battery on charging and discharging equipment under the test condition of 0.5C. The lithium-sulfur battery assembled by the diaphragm prepared by the invention has higher specific discharge capacity and more stable cycle efficiency.
Example 3
(1) Preparation of a Stable and safe separator
Accurately weighing 0.833g of Polyacrylonitrile (PAN) to dissolve in 9.0g of N, N-Dimethylformamide (DMF) solution, accurately weighing 0.167g of Chitosan (CS) to disperse in the solution, ultrasonically processing for 12h, stirring for 24h at the constant temperature of 30 ℃, then spinning the solution into a nanofiber membrane (the thickness of the membrane is 0.05 mm) on an aluminum foil by using an electrostatic spinning machine, and the specific parameters of the electrostatic spinning technology in the step (2) are as follows: a22-gauge needle is adopted, the receiving distance is 18cm, the spinning voltage is 16KV, the advancing speed is 0.1mm/min, the temperature is 30 ℃, the humidity is 50%, and the mixture is stood for 12 hours at room temperature.
And (2) carrying out pre-oxidation heating process treatment on the prepared nanofiber membrane in a muffle furnace, wherein the temperature range of the heating process is from room temperature to 120 ℃, the heating rate is 1 ℃/min, the heat preservation time at 120 ℃ is 5 hours, after heat preservation, naturally cooling to 20 ℃, taking out the material, and cutting the material into small wafers with the diameter of 19mm by using a cutting machine.
(2) Preparation of lithium-pair battery and lithium-sulfur battery
The diaphragm and two common metal lithium sheet cathodes are assembled into a CR2025 type button battery in a glove box, wherein electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was left to stand for 12 hours. Similarly, a lithium-pair battery was assembled with two lithium metal sheets and a common separator as a control.
The diaphragm, a common metal lithium sheet cathode and a sulfur positive sheet are assembled into a CR2025 type button battery in a glove box, and the electrolyte is DOL/DME =1 (volume ratio) +1M LiTFSI +0.4M LiNO 3 The assembled battery was left to stand for 12 hours. Similarly, a lithium sulfur battery was assembled by using a common separator, a lithium metal plate and a sulfur positive electrode as a control.
(3) Electrochemical performance testing of lithium on batteries
The cycle performance test of the lithium-lithium battery is carried out on the charging and discharging equipment, and the test conditions are as follows: the charging and discharging current density is 1.0mA/cm 2 And the charge and discharge amount is 1.0mAh/cm 2 . Lithium assembled with the separator prepared by the invention has smaller polarization voltage and longer and more stable cycle period for batteries.
(4) Electrochemical performance testing of lithium sulfur batteries
And (3) carrying out cycle performance test on the lithium-sulfur battery on a charging and discharging device under the test condition of 0.5C. The lithium-sulfur battery assembled by the diaphragm prepared by the invention has higher specific discharge capacity and more stable cycle efficiency.
Those skilled in the art will recognize that a wide variety of modifications, alterations, and combinations can be made with respect to the above described embodiments without departing from the scope of the invention, and that such modifications, alterations, and combinations are to be viewed as being within the ambit of the inventive concept.
Claims (10)
1. A preparation method of a high-performance chitosan/polyacrylonitrile diaphragm for a multifunctional lithium-sulfur battery is characterized by comprising the following steps:
(1) Ultrasonically dispersing chitosan powder in a polyacrylonitrile solution to form uniformly dispersed suspension;
(2) Spinning the suspension on the surface of an aluminum foil by using an electrostatic spinning technology to form an electrostatic spinning nanofiber membrane, and standing at room temperature to volatilize the solvent to form a chitosan/polyacrylonitrile fiber membrane;
(3) Heating the chitosan/polyacrylonitrile fiber membrane to convert polyacrylonitrile into preoxidized polyacrylonitrile;
(4) Drying to obtain the chitosan/polyacrylonitrile diaphragm.
2. The preparation method according to claim 1, wherein in the step (1), polyacrylonitrile (PAN) is dissolved in N, N-Dimethylformamide (DMF) solution to obtain uniformly dispersed solution, chitosan is ultrasonically dispersed in the solution for 1-12h, and magnetic stirring is carried out at constant temperature for 6-24h at room temperature to obtain uniformly dispersed suspension.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the chitosan to the polyacrylonitrile is 1 to 1; the mass concentration of the chitosan/polyacrylonitrile solution is 10-20wt%.
4. The preparation method according to claim 1, wherein in the step (2), a polyacrylonitrile fiber membrane containing chitosan is prepared by using an electrospinning technique and attached on the surface of the aluminum foil, and the membrane thickness is 0.05-0.10mm.
5. The preparation method according to claim 1, wherein in the step (3), the heating treatment is pre-oxidation treatment in a muffle furnace at 120-350 ℃, the heating rate is 1-5 ℃/min, the holding time at 120-350 ℃ is 1-5 hours, and the temperature is naturally reduced to 20-50 ℃ after holding, so that the polyacrylonitrile nano-fiber is converted into partially oxidized PAN (oxy-PAN).
6. The high-performance chitosan/polyacrylonitrile membrane for the multifunctional lithium-sulfur battery prepared by the preparation method of any one of claims 1 to 5.
7. The use of the high performance chitosan/polyacrylonitrile membrane for multifunctional lithium sulfur battery according to claim 6 in the preparation of multifunctional lithium sulfur battery.
8. The use of claim 7, wherein the button cell is assembled by the separator and two lithium metal sheet cathodes, or the button cell is assembled by the separator, the lithium metal sheet cathodes and the sulfur positive plate.
9. The application of claim 8, wherein the preparation method of the sulfur positive plate comprises the following steps: mechanically mixing sublimed sulfur, conductive carbon black and a gelatin solution according to a mass ratio of 63.
10. Use according to any one of claims 8 to 9, wherein the solvent of the battery electrolyte used is DOL/DME =1 (volume ratio) and comprises 1M LiTFSI and 0.4M LiNO 3 As a solute; the standing time of the assembled button battery is 8-12 hours; wherein the current density of the lithium pair battery is 1mA/cm 2 And (3) deposition/stripping under the condition, and carrying out charge-discharge cycle test on the lithium-sulfur battery under the condition that the multiplying power is 0.5C.
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