CN114068932B - Flexible self-doping material for lithium-sulfur battery and preparation method and application thereof - Google Patents
Flexible self-doping material for lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- CN114068932B CN114068932B CN202111172209.2A CN202111172209A CN114068932B CN 114068932 B CN114068932 B CN 114068932B CN 202111172209 A CN202111172209 A CN 202111172209A CN 114068932 B CN114068932 B CN 114068932B
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/00—Electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a flexible self-doping material for a lithium-sulfur battery and a preparation method and application thereof, the flexible self-doping material is prepared from fibrillated PBO fibers, has a three-dimensional structure, has a higher specific surface area and a rich pore structure, can better adsorb polysulfide and inhibit the shuttle of the polysulfide, can keep a higher N atom ratio after carbonization treatment, has uniform N element distribution and a very stable structure, has a very good anchoring effect on the polysulfide, can effectively improve the shuttle problem of the polysulfide, strengthens the chemical adsorption effect on the polysulfide on the basis of realizing physical barrier to polysulfide transmission, and improves the cycle capacity and the long cycle stability of the lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a flexible self-doping material for a lithium-sulfur battery and a preparation method and application thereof.
Background
Lithium sulfur batteries generally suffer from the shuttling effect of polysulfides, resulting in a decrease in capacity retention and coulombic efficiency of the battery, and a decrease in battery performance. Carbon is used as a good electron conductor, current distribution is facilitated, in addition, a porous carbon material with high specific surface area can provide a larger reaction area, electrochemical polarization of the battery is reduced, clustering of sulfur is hindered, a carbon material with high pore volume can accommodate a large amount of sulfur, and a certain physical adsorption effect is generated to inhibit lithium polysulfide Li 2 S n The carbon material has good affinity to the electrolyte of the ether lithium-sulfur battery when dissolved in the electrolyte, and can accelerate the charging and discharging of lithiumAnd (4) ion transmission. However, due to the non-polar nature of the C-C bond, pure carbon materials have poor adsorption capacity for polar lithium polysulfides, which are easily lost from the positive carbon network. In order to increase the polarity of the carbon material and make the carbon material have a binding effect on lithium polysulfide, researchers often perform heteroatom doping treatment on the carbon material, and the carbon material surface is rich in polar groups after the heteroatom doping, so that the effect of fixing the lithium polysulfide can be achieved 3 Or soaking the prepared sample in solution of urea, ammonium chloride, etc. for a period of time, and treating with tubular furnace. Chinese patent CN106684389A discloses a sulfur-nitrogen double-doped graphene nano material and a preparation method and application thereof, wherein a sandwich structure material for a lithium-sulfur battery is prepared by carbonizing oxidized graphene and thiourea, but due to the complex doping process and the uneven distribution of N elements, the N elements can be removed in the circulating process, so that the shuttle effect of the lithium-sulfur battery cannot be avoided, and the performance of the battery is reduced.
Disclosure of Invention
The invention aims to solve the technical problems that the interlayer of the existing lithium-sulfur battery cannot avoid the shuttle effect, so that the performance of the battery is reduced, and the invention provides a flexible self-doping material for the lithium-sulfur battery, which is prepared from fibrillated PBO fibers, has higher specific surface area and abundant pore structures, has good adsorption effect, can effectively inhibit the shuttle of polysulfide, is used as the interlayer of the lithium-sulfur battery, is favorable for electron and ion transmission, improves the electrolyte wettability, and improves the ionic conductivity and coulombic efficiency of the battery, thereby ensuring the performance of the battery.
It is yet another object of the present invention to provide a method of preparing a flexible self-doping material for a lithium sulfur battery.
It is another object of the present invention to provide a use of a flexible autodoping material for a lithium sulfur battery.
The above purpose of the invention is realized by the following technical scheme:
a flexible self-doping material for a lithium-sulfur battery, comprising fibrillated PBO fibers, the flexible self-doping material having a specific surface area of 100-2600g/m 2 The quantitative ratio is 30-100g/m 2 The thickness is 40-160um.
The invention utilizes the fibrillated PBO (poly-p-phenylene benzobisoxazole) fiber to prepare the flexible self-doping material, because the PBO fiber contains N and can still keep higher N content after high-temperature activation and carbonization, the self-doped N atoms can be uniformly distributed in a carbon skeleton, the fibrillated PBO fiber has higher specific surface area and abundant pore structures, the charge density of a carbon material can be enhanced, the adsorption performance to polysulfide can be improved, and the fibrillated PBO fiber can still keep higher ratio after high-temperature treatment, can be used as an interlayer material, is applied to a lithium sulfur battery, inhibits the shuttling of the polysulfide, can obviously improve the capacity retention rate and the coulombic efficiency of the battery, and improves the battery performance.
Preferably, the fibrillated PBO fibers have a diameter of 100-1000nm.
Preferably, the basis weight is 30 to 50g/m 2 The thickness is 40-70um.
The invention protects the preparation method of the flexible self-doping material for the lithium-sulfur battery, which comprises the following steps:
s1, fully defibering fibrillated PBO fibers, and adding water to dilute to a sheet making concentration of 0.02wt% -0.05wt% to obtain slurry;
s2, manufacturing and forming the slurry obtained in the step S1 to obtain a wet paper web;
s3, drying the wet paper web obtained in the step S2 at the temperature of 100-150 ℃ for 5-10min to obtain a dry paper web;
s4, performing calendaring treatment on the dry paper web in the step S3 at the temperature of 180-200 ℃ for 5-10min;
and S5, carbonizing the material subjected to the calendaring treatment in the step S4 to obtain the flexible self-doping material for the lithium-sulfur battery.
Preferably, the carbonization of step S5 is one of direct carbonization, physical activation carbonization, and chemical activation carbonization.
Preferably, the direct carbonization is that the material calendered in the step S4 is heated to 500-600 ℃ under the protection of nitrogen and is kept for 1-2 hours; then continuously introducing nitrogen, heating to 850-1000 ℃, preserving the heat for 50-60min at the temperature of 850-1000 ℃, and then cooling to normal temperature to obtain the flexible self-doping material.
Preferably, the physical activation carbonization is that the material calendered in the step S4 is heated to 500-600 ℃ under the protection of nitrogen, the temperature is kept for 1-2h, then carbon dioxide is introduced, the temperature is heated to 850-1000 ℃, the temperature is kept at 850-1000 ℃ for 50-60min, and then the material is cooled to normal temperature, so that the flexible self-doping material is obtained.
Preferably, the chemical activation carbonization is to soak the material calendered in the step S4 in KOH solution, heat the material to 500-600 ℃ under the protection of nitrogen, preserve heat for 1-2h, then continuously introduce nitrogen, heat the material to 850-1000 ℃, preserve heat for 50-60min at 850-1000 ℃, and then cool the material to normal temperature to obtain the flexible self-doping material.
Preferably, the PBO fibrillated fibers in step S1 have a freeness of 75 to 92 ° SR after dilution with water.
Preferably, the paper making and forming in step S2 are performed in a former.
Preferably, step S2 further comprises, before making paper, sieving and rectifying the slurry to make the slurry present a highly turbulent flow state.
Preferably, the drying process of step S3 is performed in a tumble dryer.
Preferably, the calendering process of step S4 is performed using a metal roll and a soft roll.
Preferably, the fibrillated PBO fibers are prepared by a method comprising: PBO chopped fibers are soaked for 6 hours according to the concentration of 2wt%, a groove type beater is used for fibrillation treatment, and PBO fibers are subjected to cortex removal and splitting to complete fibrillation. The groove type beater cuts, crushes, kneads, splits, soaks and refines the PBO fiber slurry through the mechanical action generated by the fly cutter roller and the bottom knife. The fibrillation fiber with the beating degree of 40-69 DEG SR can be obtained by controlling the counter flow speed of 0.03-0.15 m/s and the beating time of 1-1000 h. The fibrillation process of PBO ensures proper length, diameter and fibrillation degree through process controlAnd the uniform dispersion and formation of the fibrillated superfine fibers are ensured by 0.05 percent of sizing and 0.1 percent of forming concentration in the forming process, the control on the structure and the uniformity of the paper base material is enhanced in the high-speed turbulent motion process, the fibrillated superfine fibers are uniformly distributed and tightly combined, the dimensional stability of the base material is improved, and the flow rate is 100-160m 3 The/h and the concentration of 0.01wt% -0.1wt% are controlled to realize the quantitative regulation and control of the self-supporting material base material in a larger proportion range, and the base material structure is efficiently and flexibly regulated.
The invention protects the application of the flexible self-doping material for the lithium-sulfur battery in the preparation of the lithium-sulfur battery.
A lithium-sulfur battery interlayer material is prepared from the flexible self-doping material for the lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that:
the flexible self-doping material provided by the invention is prepared from fibrillated PBO fibers, has a three-dimensional structure, has a higher specific surface area and a rich pore structure, can better adsorb polysulfide and inhibit the shuttle of the polysulfide, can keep a higher N atomic ratio after carbonization treatment, has a very stable structure, has a very good anchoring effect on the polysulfide, can effectively improve the shuttle problem of the polysulfide, strengthens the chemical adsorption effect on the polysulfide on the basis of realizing physical barrier to polysulfide transmission, and improves the cycle capacity and the long cycle stability of a lithium-sulfur battery.
Drawings
Fig. 1 is a schematic diagram of a lithium sulfur battery according to the present invention using a flexible autodoping material of example 1.
FIG. 2 is an electron microscope image of the flexible autodoped material prepared in example 1 of the present invention.
Fig. 3 is a physical diagram of the flexible self-doping material prepared in example 1 of the present invention.
FIG. 4 is an electron microscope image of 2000 times magnification of the flexible autodoped material prepared by the direct carbonization method in example 1 of the present invention.
FIG. 5 is an electron microscope image of 10000 times magnified flexible autodoped material prepared by direct carbonization in example 1 of the present invention.
Fig. 6 is a picture of a flexible self-doping material object bent by a direct carbonization method in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The following examples and comparative examples use the starting materials:
PBO chopped fiber, dongli, japan, AS-6mm.
PBO fibrillated fibers: PBO chopped fibers are soaked for 6 hours according to the concentration of 2wt%, a groove type beater is used for fibrillation treatment, and PBO fibers are subjected to cortex removal and splitting to complete fibrillation. The groove type beater cuts off, crushes, kneads, splits, moistens and refines the PBO fiber slurry through the mechanical action generated by the fly cutter roller and the bottom cutter. The flow speed is 0.15m/s, and the PBO fibrillated fiber with the beating degree of 69 DEG SR can be obtained after beating for 1000 hours.
Example 1
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery comprises the following steps:
s1, preparing slurry and delivering
After the PBO chopped fibers are fibrillated, the fibrillated PBO fibers are mixed, dispersed and diluted with water in a fiber fluffer, and the concentration of the fibrillated PBO fibers in percentage by weight is 0.02 percent of the concentration of sheet making, so that slurry is obtained;
s2, papermaking forming
Feeding the slurry into a vacuum sheet making machine for making and forming to obtain a wet paper web;
s3, obtaining wet paper sheets through dehydration treatment, and drying the wet paper sheets for 10min at the temperature of 150 ℃ in a Yankee cylinder to obtain dry paper webs;
s4, performing hot-press polishing treatment on the metal roller and the elastic roller at the temperature of 200 ℃ for 10min;
s5, carbonizing
And (3) putting the material calendered in the step (S4) into a tubular furnace, heating to 600 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen, preserving heat for 1h, then heating from 600 ℃ to 850 ℃ at the heating rate of 8 ℃/min, preserving heat for 60min at 850 ℃, and then cooling to normal temperature to obtain the self-supporting material.
Example 2
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery is different from that of the embodiment 1 in that S5: and (4) putting the material calendered in the step (S4) into a tubular furnace, heating to 600 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen, then heating to 1000 ℃ from 600 ℃ at the heating rate of 8 ℃/min, preserving the heat at 1000 ℃ for 60min, and then cooling to normal temperature to obtain the activated carbon fiber.
Example 3
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery is different from that of the embodiment 1 in that S5: activating by using a physical activation carbonization method, namely, firstly, heating to 600 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, and preserving heat for one hour; and in the second stage, introducing carbon dioxide, raising the temperature to 850 ℃ at the heating rate of 8 ℃/min, preserving the temperature for 60min at the temperature of 850 ℃, and then cooling to the normal temperature.
Example 4
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery is different from that of the embodiment 1 in that S5: activating by using a physical activation carbonization method, namely, firstly, heating to 600 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, and preserving heat for one hour; and in the second stage, introducing carbon dioxide, raising the temperature to 1000 ℃ at the heating rate of 8 ℃/min, preserving the temperature for 60min at the temperature of 1000 ℃, and then cooling to the normal temperature.
Example 5
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery is different from that of the embodiment 1 in that S5: activating by using a chemical activation carbonization method, and carbonizing in two steps after soaking by using a KOH solution, wherein in the first step, the temperature is increased to 600 ℃ at the temperature rise rate of 10 ℃/min under the protection of nitrogen, and the temperature is kept for one hour; in the second stage, the temperature is raised to 850 ℃ at the heating rate of 8 ℃/min, the temperature is kept at 850 ℃ for 60min, and then the temperature is cooled to the normal temperature.
Example 6
A flexible autodoping material for a lithium sulfur battery comprising fibrillated PBO fibers, the specific surface area, basis weight, and thickness of the flexible autodoping material are shown in table 1 below.
The preparation method of the flexible self-doping material for the lithium-sulfur battery is different from that of the embodiment 1 in that S5: activating by using a chemical activation carbonization method, and carbonizing in two steps after soaking by using a KOH solution, wherein in the first step, the temperature is increased to 600 ℃ at the temperature rise rate of 10 ℃/min under the protection of nitrogen, and the temperature is kept for one hour; in the second stage, the temperature is raised to 1000 ℃ at the heating rate of 8 ℃/min, the temperature is kept at 1000 ℃ for 60min, and then the temperature is cooled to the normal temperature.
Comparative examples 1 to 2
Comparative example 1 is a material prepared by carbonizing a softwood paper-based material doped with urea, 95% pure, from Guangzhou chemical reagent works; the needle-leaved wood paper base material is prepared by selecting a sunshine Senbo brand needle-leaved wood pulp board in a Shandong Asia Taisen Bo pulp factory, and carbonizing the needle-leaved wood pulp board in a tubular furnace at 500 ℃ after sheet forming.
Comparative example 2 differs from example 1 in that it was made using a non-fibrillated PBO fiber material.
Performance testing
1. Test method
(1) Quantification of
Measured using TAPPI standards.
(2) Average pore diameter of fiber
Measured using a fiber analyzer.
(3) Appearance of flexible self-doping material
And testing and analyzing the appearance and the pore structure of the diaphragm by using a scanning electron microscope.
(4) Elemental analysis
The content of C, N, O was tested using an elemental analyzer.
(5) Constant current charge and discharge test
Respectively using the flexible self-doping materials prepared in the above examples 1 to 6 as the PBO flexible interlayer and the materials prepared in the comparative examples 1 to 2 as the flexible interlayer, assembling the lithium-sulfur battery in the sequence of the negative electrode case → the lithium sheet → the diaphragm → the electrolyte (40 μ L) → the PBO flexible interlayer → the positive electrode sheet → the steel sheet → the spring sheet → the positive electrode case, and finally sealing the battery packaging machine, wherein the battery assembly is completed as shown in fig. 1. In addition, the lithium-sulfur battery without the interlayer is assembled for comparison, and a battery test cabinet is adopted to test the specific capacity, the coulomb efficiency, the cycle life and the rapid charge and discharge capacity of the battery. All the assembled batteries were left for 6h before testing and were charged and discharged with a constant current, the range of charge and discharge being 1.7-2.6V.
2. Test results
TABLE 1 elemental analysis data for free-standing materials of different carbonization activation processes
| Sample (I) | N(wt％) | C(wt％) | H(wt％) | S(wt％) |
| Example 1 | 7.11 | 80.64 | 1.3 | 0 |
| Example 2 | 6.62 | 78.53 | 1.22 | 0 |
| Example 3 | 6.58 | 77.92 | 1.16 | 0 |
| Example 4 | 6.01 | 75.33 | 1.03 | 0 |
| Example 5 | 4.64 | 62.84 | 0.58 | 0 |
| Example 6 | 3.52 | 60.1 | 0.36 | 0 |
Table 1 shows that by comparing the contents of C, N, H and S elements in PBO fibrillated fiber, direct carbonization, physically activated carbonization and chemically activated carbonization, the N content is still high after carbonization, wherein the N content after direct carbonization is higher than that of CO 2 Activating carbonization treatment and KOH activating carbonization. The doping of the N element can lead the surrounding carbon atoms to be electropositive, and more defects and active sites are introduced into a carbon skeleton, so that the interface adsorption capacity is improved, and therefore, the fibrillated PBO fiber self-doped with N can lead the flexible self-doped material to have specific adsorption removal performance.
TABLE 2 BET data for flexible autodoped materials for different carbonization activation processes
As shown in Table 2, the flexible autodoped materials prepared in examples 1-6 of the present invention have a high specific surface area, and the specific surface area after KOH activation and carbonization is higher than that of CO 2 The activated carbonization and the direct carbonization have better adsorption effect on polysulfide, but the strength of the flexible material subjected to the direct carbonization is better, and the N retention rate is the highest at the same temperature as shown in the table 1.
Table 3 coulombic efficiency comparison for lithium sulfur batteries prepared using flexible autodoping materials
As seen from table 3, in embodiments 1 to 6 of the present invention, the PBO fibrillated fibers are adopted to prepare the lithium sulfur battery sandwich structure, and the PBO fibrillated fibers have a self-supporting structure, a high specific surface area, and a high N content, so that a strong adsorption effect of a self-supporting material is ensured, and a better technical guarantee is provided for inhibiting a shuttle effect of polysulfide of the lithium sulfur battery, so that the flexible autodoped material prepared by the present invention is used as the sandwich layer to prepare the lithium sulfur battery, and can significantly improve a capacity retention rate and a coulomb efficiency of the battery, a specific capacity after 100 cycles at a rate of 0.2C is maintained at more than 80% of an initial specific capacity, and both the specific capacity and the coulomb efficiency exceed 920mAh/g, and the coulomb efficiency is more than 99%.
The method for doping the N element in the comparative example 1 has the advantages of relatively complex process, uneven distribution of the N element, low doping proportion, easy introduction of other impurities, removal in the circulating process and influence on the performance of the battery. Comparative example 2, pbo unfibrillated paper base material became a chip state after carbonization, could not be bent at will, and had a thickness as high as 300um, affecting the cycle performance of lithium sulfur batteries, and the steel bar structure of the surface was not rich in porosity to adsorb polysulfides. The lithium-sulfur battery without the interlayer can not effectively adsorb polysulfide, and the cycle performance of the lithium-sulfur battery is poor and is easy to attenuate.
In figure 2, the PBO fibrillated fibers after 1000h beating are seen to be intertwined with each other to form a compact paper-based structure. Figure 3 shows that the PBO fibrillated fibers after 1000h beating have a very flat surface and uniform fiber distribution.
As can be seen from fig. 4 and 5, the PBO fibrillated fiber still maintains an intact micro-nano structure after being directly carbonized at 900 ℃. As can be seen from fig. 6, the PBO fibrillated fiber can be bent to a large extent by external force after being directly carbonized, and has a flat surface.
The PBO fibrillated fiber is adopted to prepare the flexible self-supporting material, the specific surface area is high, the PBO fibrillated fiber has a multi-level pore structure and good flexibility, and the PBO fibrillated fiber is used as a lithium-sulfur battery interlayer and can adsorb a large amount of lithium polysulfide, so that the stability of lithium polysulfide clusters is ensured, the lithium polysulfide clusters are prevented from being dissolved in electrolyte, the shuttle effect of polysulfide can be inhibited, and the battery performance is ensured.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (3)
1. The lithium-sulfur battery interlayer material is characterized in that the specific surface area of the lithium-sulfur battery interlayer material is 100-2600g/m 2 The quantitative ratio is 30-100g/m 2 The thickness is 40-160um;
the preparation method of the lithium-sulfur battery interlayer material comprises the following steps:
s1, fully defibering fibrillated PBO fibers, and adding water to dilute to a sheet making concentration of 0.02wt% -0.05wt% to obtain slurry;
s2, manufacturing and forming the slurry obtained in the step S1 to obtain a wet paper web;
s3, drying the wet paper web obtained in the step S2 at the temperature of 100-150 ℃ for 5-10min to obtain a dry paper web;
s4, performing calendaring treatment on the dry paper web in the step S3 at the temperature of 180-200 ℃ for 5-10min;
s5, carbonizing the material subjected to the calendaring treatment in the step S4 to obtain a lithium-sulfur battery interlayer material;
step S5, the carbonization is one of direct carbonization, physical activation carbonization and chemical activation carbonization;
the direct carbonization is that the material calendered in the step S4 is heated to 500-600 ℃ under the protection of nitrogen, and the temperature is kept for 1-2h; then continuously introducing nitrogen, heating to 850-1000 ℃, preserving the heat for 50-60min at the temperature of 850-1000 ℃, and then cooling to normal temperature to obtain the lithium-sulfur battery interlayer material;
in the physical activation carbonization, the material calendered in the step S4 is heated to 500-600 ℃ under the protection of nitrogen, is subjected to heat preservation for 1-2h, is introduced with carbon dioxide, is heated to 850-1000 ℃, is subjected to heat preservation for 50-60min at the temperature of 850-1000 ℃, and is cooled to normal temperature to obtain the lithium-sulfur battery interlayer material;
and the chemical activation carbonization is to soak the material calendered in the step S4 in KOH solution, heat the material to 500-600 ℃ under the protection of nitrogen, preserve the heat for 1-2h, then continuously introduce nitrogen, heat the material to 850-1000 ℃, preserve the heat for 50-60min at the temperature of 850-1000 ℃, and then cool the material to the normal temperature to obtain the lithium-sulfur battery interlayer material.
2. The lithium sulfur battery sandwich material of claim 1 wherein the fibrillated PBO fibers have a diameter of 100-1000nm.
3. The lithium sulfur battery sandwich material of claim 1, wherein the basis weight is 30-50g/m 2 The thickness is 40-70um.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2395692A1 (en) * | 1995-03-31 | 1996-10-03 | Mitsubishi Paper Mills Limited | Nonwoven fabric for separator of non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004288495A (en) * | 2003-03-24 | 2004-10-14 | Tomoegawa Paper Co Ltd | Electrolyte film for polymer electrolyte fuel cell and manufacturing method of the same |
| US8252449B2 (en) * | 2004-04-16 | 2012-08-28 | Mitsubishi Paper Mills Limited | Separator for electrochemical element |
| CN1683712A (en) * | 2005-03-11 | 2005-10-19 | 华南理工大学 | PBO fiber paper base material and its preparing method and use |
| CN102522515A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/polymer fiber composite diaphragm material for lithium secondary battery and preparation method thereof |
| WO2014113944A1 (en) * | 2013-01-23 | 2014-07-31 | 华南理工大学 | Diaphragm paper, and preparation method and application thereof |
| JP2018133141A (en) * | 2017-02-13 | 2018-08-23 | 東洋紡株式会社 | Redox battery using thin diaphragm |
| JP7156819B2 (en) * | 2018-05-18 | 2022-10-19 | 三菱製紙株式会社 | Base material for lithium ion battery separator and lithium ion battery separator |
| CN110148696B (en) * | 2019-05-10 | 2020-07-21 | 浙江大学 | Diaphragm capable of preventing lithium dendrite and rechargeable lithium battery |
| EP3979357A4 (en) * | 2019-05-29 | 2023-03-01 | Daicel Corporation | Slurry |
| CN111082063B (en) * | 2019-12-26 | 2023-03-28 | 内蒙古民族大学 | Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery |
| CN112726283B (en) * | 2020-12-25 | 2022-09-06 | 烟台民士达特种纸业股份有限公司 | Poly (p-phenylene benzobisoxazole) fiber paper base material for high-temperature-resistant honeycomb core material and preparation method thereof |
| CN113270622A (en) * | 2021-04-28 | 2021-08-17 | 中国石油大学(北京) | Polymer-based double-layer nanofiber composite proton exchange membrane and preparation method thereof |
-
2021
- 2021-10-08 CN CN202111172209.2A patent/CN114068932B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2395692A1 (en) * | 1995-03-31 | 1996-10-03 | Mitsubishi Paper Mills Limited | Nonwoven fabric for separator of non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
Non-Patent Citations (2)
| Title |
|---|
| PBO纤维的性能及应用;刘丹丹等;《合成纤维工业》;20051031;第28卷(第5期);第43-46页 * |
| 聚烯烃纤维电池隔膜纸的研究;刘希夷等;《中国造纸》;20070325(第03期);第15-17页 * |
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