LU501569B1 - Preparation method of flame-retardant all-solid-state battery electrolyte membrane - Google Patents
Preparation method of flame-retardant all-solid-state battery electrolyte membrane Download PDFInfo
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- LU501569B1 LU501569B1 LU501569A LU501569A LU501569B1 LU 501569 B1 LU501569 B1 LU 501569B1 LU 501569 A LU501569 A LU 501569A LU 501569 A LU501569 A LU 501569A LU 501569 B1 LU501569 B1 LU 501569B1
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- electrolyte membrane
- flame
- preparation
- retardant
- electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000005119 centrifugation Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- 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 5
- 238000001035 drying Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 35
- 210000002966 serum Anatomy 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The disclosure discloses a flame-retardant all-solid-state battery electrolyte membrane and a preparation method thereof. The preparation method comprises: putting a product in an organic solvent for ultrasonic smashing and centrifugation after black phosphorus is subjected to electrochemical assisting method treatment to obtain a dispersion of a flame-retardant material; adding the dispersion into PEO-based electrolyte powder, and performing constant-temperature stirring to obtain a polymer solution; then pouring the polymer solution into an electrolyte membrane forming mold; and finally sequentially putting the mold in a deaerating plant and a vacuum drying box to be dried to prepare the electrolyte membrane. The flame-retardant material needed by the disclosure is of a two-dimensional structure, in the preparation method of the disclosure, the electrolyte membrane can have excellent flame-retardant capacity even when a small quantity of the material is added, and the conductivity of the electrolyte membrane can be improved.
Description
BL-5429
LU501569
PREPARATION METHOD OF FLAME-RETARDANT ALL-SOLID-STATE
BATTERY ELECTROLYTE MEMBRANE
[01] The disclosure belongs to the technical field of lithium ion battery solid-state electrolyte, and particularly relates to a preparation method of a flame-retardant all-solid-state battery electrolyte membrane.
[02] Lithium ion batteries (LIBs) have been widely applied to the fields such as portable electronic devices, electric automobiles and energy storage since its successful commercialization in 1991. At present, the commercial LIBs mostly adopt carbonic ester electrolyte, but this electrolyte is poor in oxidation resistance, inflammable and leaky, so that the LIBs have serious safety problems such as leakage, ignition and explosion.
[03] The above problems can be effectively solved by adopting solid-state electrolyte, but the solid-state electrolyte is poor in ionic conductivity and wettability on electrodes at present.
Usually, interface contact between inorganic solid-state electrolyte and electrodes is poor, and interface impedance is large. Polymer electrolyte has good film forming performance and flexibility, well makes contact with the electrodes, has a controllable size, and shows good application prospects. But the existing polymer electrolyte has the defects of being low in conductivity and inflammable. Thus, one of hot spots of researching all-solid-state polymer electrolyte at present is to develop a solid-state electrolyte membrane with high ionic conductivity and good flame retardance.
[04] The disclosure selects a nano two-dimensional material: black phosphorene as a flame retardant, and the flame retardant can have good flame retardance even when a small quantity is added due to its special microstructure and composition.
[05] Based on the above, it is urgent to explore a solid-state electrolyte membrane with good flame retardance and high ionic conductivity and a preparation method thereof.
[06] The disclosure provides a flame-retardant all-solid-state battery electrolyte membrane and a preparation method thereof aimed to the above technical problems.
[07] A preparation method of a flame-retardant all-solid-state battery electrolyte membrane, characterized in that the preparation method comprises the following steps:
[08] SI: putting black phosphorus in an organic solvent for ultrasonic smashing and centrifugation after the black phosphorus is subjected to electrochemical assisting method treatment to obtain a dispersion of a flame-retardant material;
[09] S2: adding PEO-based electrolyte powder into the dispersion in S1, performing constant-temperature stirring, and fully dissolving the materials to obtain a polymer solution;
BL-5429
LU501569 and
[10] S3: pouring the polymer solution prepared in S2 into an electrolyte membrane forming mold, and sequentially putting the mold in a deaerating plant and a vacuum drying box to be dried to prepare an electrolyte membrane.
[11] Optionally, an electrochemical assisting method comprises the following steps:
[12] (1) weighing 0.01-0.1 g of black phosphorus as an anode, taking a platinum net as a counter electrode, and assembling the black phosphorus, the platinum net and electrolyte into an electrolytic tank; and
[13] (2) reacting at the voltage of 3-10 V.
[14] Optionally, the mass of the flame-retardant material in S1 accounts for 0.03%o-0.06%o that of the organic solvent; and the organic solvent is one of DMF and NMP.
[15] Optionally, time and frequency of cell smashing in S1 are 80-120 min and 20-33 Hz respectively; and speed and time of centrifugation are 3000-8000 r/min and 10-20 min respectively.
[16] Optionally, the mass of the PEO-based electrolyte powder in S2 accounts for 6%-12% that of the polymer solution.
[17] Optionally, the PEO-based electrolyte powder in S2 is prepared by mixing PEO, PVDE,
Al,Os and LiTFSI in a certain ratio.
[18] Optionally, a fully-dissolving method in S2 comprises the following steps: stirring for 4-6 hat constant temperature of 50-70 degrees Celsius and stirring speed of 50-200 r/min.
[19] Optionally, a drying method in S3 comprises the following steps: putting the mold in the deaerating plant to be dried for 3-8 h at constant temperature of 50-70 degrees Celsius, and then putting the mold in the vacuum drying box to be dried for 3-6 h at constant temperature of 30-60 degrees Celsius.
[20] The present disclosure has the following beneficial effects:
[21] In the disclosure, the used flame-retardant material is a nano-scale two-dimensional material: black phosphorene only contains phosphorus with the flame-retardant effect, its flame-retardant effect is high, the smoke emission in the combustion process is small, and the toxicity is low. Due to the size characteristic of the black phosphorene, the interface interaction of the black phosphorene flame retardant and a polymer is large, the compatibility of the polymer and the black phosphorene can be improved, and compared with a Nano flame- retardant material, the heat stability and the flame retardance of the compounded material are both greatly improved. In addition, an effective ion transmission network is formed in electrolyte by the two-dimensional lamellar structure, and the two-dimensional lamellar structure also can serve as an additive for improving the electrical performance of the electrolyte.
The black phosphorene flame retardant is an ideal electrolyte flame-retardant additive.
BL-5429 . , . Cs . . LU501569
[22] Finally, the material is easily oxidatively degraded to fail due to its nano two- dimensional structure, and the drying method provided by the disclosure can effectively relieve the problem of oxidative degradation failure of the flame-retardant material.
[23] Based on the above, compared with the prior art, the material can simultaneously meet the requirements of improving the heat stability and the electrical performance of the electrolyte to a large degree under a low adding quantity.
[24] FIG. 1 is a diagram of conductivity test data of solid-state electrolyte prepared in embodiments 1 and 2 and comparative examples 1, 2 and 3;
[25] FIG. 2 is a diagram of TG test data of solid-state electrolyte prepared in embodiments 1 and 2 and comparative examples 1 and 2.
[26] FIG. 3 is a diagram of DSC test data of solid-state electrolyte prepared in embodiments 1 and 2 and comparative examples 1 and 2.
[27] To make the objectives, technical solutions, and advantages of the embodiments of the disclosure clearer, the following clearly and completely describes the technical solutions in the embodiments of the disclosure with reference to the accompany drawings in the embodiments of the disclosure. Based on the embodiments in the disclosure, all other embodiments obtained by those ordinarily skilled in the art without involving creative labor all belong to the protection scope of the disclosure.
Embodiment 1
[28] A preparation method of a flame-retardant all-solid-state battery electrolyte membrane, comprises the following steps:
[29] (1) 0.02 g of black phosphorus is weighed as an anode, a platinum net is taken as a counter electrode, and the black phosphorus, the platinum net and electrolyte are assembled into an electrolytic tank.
[30] (2) reacting is performed at the voltage of 9 V.
[31] (3) a product is added into DMF for ultrasonic smashing and centrifugation to obtain a black phosphorene dispersion.
[32] (4) 1.6gof PEO, 0.6 g of PVDF, 0.3 g of Al,O3 and 0.8 g of LiTFSI are weighed and put in a serum bottle for use.
[33] (5) 30 ml of dispersion in step (3) is added into the serum bottle in step (4), stirred at constant temperature of 50 degrees Celsius and rotating speed of 100 r/min, and fully dissolved to obtain a polymer solution.
BL-5429 a . . . — LU501569
[34] (©) the polymer solution in step (5) is poured into an electrolyte membrane forming mold, and the mold is put in a deaerating plant to be dried for 3 h at constant temperature of 55 degrees Celsius and then put in a vacuum drying box to be dried for 4 h at constant temperature of 45 degrees Celsius to prepare the electrolyte membrane.
Embodiment2
[35] A preparation method of a flame-retardant all-solid-state battery electrolyte membrane, comprises the following steps:
[36] (1) 0.05g of black phosphorus is weighed as an anode, a platinum net is taken as a counter electrode, and the black phosphorus, the platinum net and electrolyte are assembled into an electrolytic tank.
[37] (2) reacting is performed at the voltage of 9 V.
[38] (3) a product is added into DMF for ultrasonic smashing and centrifugation to obtain a black phosphorene dispersion.
[39] (4) 1.6 gof PEO, 0.6 g of PVDF, 0.3 g of ALOs and 0.8 g of LiTFSI are weighed and putin a serum bottle for use.
[40] (5) 30 ml of dispersion in step (3) is added into the serum bottle in step (4), stirred at constant temperature of 50 degrees Celsius and rotating speed of 100 r/min, and fully dissolved to obtain a polymer solution.
[41] (©) the polymer solution in step (5) is poured into an electrolyte membrane forming mold, and the mold is put in a deaerating plant to be dried for 3 h at constant temperature of 55 degrees Celsius and then put in a vacuum drying box to be dried for 4 h at constant temperature of 45 degrees Celsius to prepare the electrolyte membrane.
Embodiment 3
[42] Comparative example 1: the comparative example 1 is a comparative example of the embodiment 2, and the comparative example 1 mainly differs from the embodiment 2 that no flame-retardant material is added into step (1). A preparation method of an electrolyte membrane in the comparative example comprises the following steps:
[43] (1) 1.6 gof PEO, 0.6 g of PVDF, 0.3 g of ALOs and 0.8 g of LiTFSI are weighed and put in a serum bottle for use.
[44] (2) 30 ml of DMF is taken and added into a serum bottle in step (1), stirred at constant temperature of 50 degrees Celsius and rotating speed of 100 r/min, and fully dissolved to obtain a polymer solution.
[45] (3) the polymer solution in step (2) is poured into an electrolyte membrane forming mold, and the mold is put in a deaerating plant to be dried for 3 h at constant temperature of 55 degrees Celsius and then put in a vacuum drying box to be dried for 4 h at constant temperature of 45 degrees Celsius to prepare the electrolyte membrane.
BL-5429
LU501569
Embodiment 4
[46] Comparative example 2: the comparative example 2 is a comparative example of the embodiment 2, and the comparative example 2 mainly differs from the embodiment 2 that the mold is not dried in the deaerating plant in step (6). À preparation method of an electrolyte 5 membrane in the comparative example comprises the following steps:
[47] (1) 0.05g of black phosphorus is weighed as an anode, a platinum net is taken as a counter electrode, and the black phosphorus, the platinum net and electrolyte are assembled into an electrolytic tank.
[48] (2) reacting is performed at the voltage of 9 V.
[49] (3) aproductis added into DMF for ultrasonic smashing and centrifugation to obtain a black phosphorene dispersion.
[50] (4) 1.6 gof PEO, 0.6 g of PVDF, 0.3 g of ALOs and 0.8 g of LITFSI are weighed and put in a serum bottle for use. [S51] (5) the dispersion in step (3) is added into the serum bottle in step (1), stirred at constant temperature of 50 degrees Celsius and rotating speed of 100 r/min, and fully dissolved to obtain a polymer solution.
[52] (6) the polymer solution in step (2) is poured into an electrolyte membrane forming mold, and the mold is put in a vacuum drying box to be dried for 4 h at constant temperature of 45 degrees Celsius to prepare the electrolyte membrane.
Embodiment 5
[53] Comparative example 3: the comparative example 3 is a comparative example of the embodiment 2, the comparative example 3 mainly differs from the embodiment 2 that a flame- retardant material red phosphorus is added into step (1), and a preparation method of polymer electrolyte in the comparative example comprises the following steps:
[54] (1)0.05 g of red phosphorus is taken and added into 50 ml of absolute ethyl alcohol to be dissolved to obtain a dispersion.
[55] (2) 1.6 gof PEO, 0.6 g of PVDF, 0.3 g of ALOs and 0.8 g of LITFSI are weighed and put in a serum bottle for use.
[56] (3) 3ml of dispersion in step (1) is added into the serum bottle in step (2), stirred at constant temperature of 50 degrees Celsius and rotating speed of 100 r/min, and fully dissolved to obtain a polymer solution.
[57] (4) the polymer solution in step (3) is poured into an electrolyte membrane forming mold, and the mold is put in a deaerating plant to be dried for 3 h at constant temperature of 55 degrees Celsius and then put in a vacuum drying box to be dried for 4 h at constant temperature of 45 degrees Celsius to prepare the electrolyte membrane.
BL-5429 . LU501569
Embodiment 6
[58] Performance test
[539] (1) Conductivity test
[60] Flame-retardant all-solid-state battery electrolyte membranes prepared in the embodiments 1 and 2 and the comparative examples 1, 2 and 3 are clamped between two stainless steel sheets respectively, ionic conductivity is tested, the test frequency range is 10
Hz-10° Hz, and specific test results are listed in Table 1 and FIG. 1.
Table 1 Conductivity test table
Sample name Conductivity /S/cm
Embodiment 1 1.802x10*
Embodiment 2 2.954x10*
Comparative Example 1 1.548x10*
Comparative Example 2 1.457x10*
Comparative Example 3 0.820x107
[61] Seen from Table 1, the conductivity of the electrolyte membrane in the comparative example 3 is reduced relative to the comparative example 1, the conductivity of the electrolyte membranes in the embodiment 1 and the embodiment 2 is increased to a certain degree relative to the comparative example 1, and it is shown that red phosphorus in a phosphorus flame- retardant material with the same adding quantity has an adverse effect on the electrical performance of the electrolyte membrane, but black phosphorene can improve the electrochemical performance of the electrolyte membrane.
[62] (2) Flame-retardant performance test
[63] The embodiment 1 and 2 and the comparative examples 1 and 2 are subjected to thermogravimetric test.
[64] 4-8 mg of samples of the embodiments 1 and 2 and the comparative examples 1 and 2 are weighed and put in a crucible, and the mass change of the samples is measured in the continuous heating process, wherein test atmosphere is nitrogen, test temperature is room temperature of 800 degrees Celsius, heating speed is 10 degrees Celsius/min, and specific results are listed in FIG. 2 and FIG. 3.
[65] Seen from FIG. 2, the maximum residual carbon quantity in the embodiment 2 is 23%, and decomposition temperature reaches up to 349 degrees Celsius. The residual carbon quantities of the electrolyte membranes under four conditions sequentially are: embodiment 2 > embodiment 1 > comparative example 2 > comparative example 1 from large to small, and it is shown that the flame retardance of the electrolyte membranes is improved to a certain degree by adding a small quantity of black phosphorene, and the improving effect is improved along with increase of the adding quantity. The black phosphorene does not play a role in improving the flame retardance in electrolyte membranes not subjected to deaerating treatment, and it is shown that the deaerating step is necessary.
BL-5429 ; LU501569
[66] The embodiments 1 and 2 and the comparative examples 1 and 2 are subjected to limit oxygen index test.
[67] Prepared membranes are cut into 1 cm * 10 cm long strips, each membrane is cut into 5-10 strips, 5 cm positions are marked, then an experimental facility is adjusted into an experimental state, the volume fraction of oxygen is controlled by adjusting the oxygen content and the nitrogen content in each test, then the strip-shaped membranes are ignited in oxygen- nitrogen mixed airflow, combustion states and combustion time are recorded, and the minimum oxygen concentration, namely limit oxygen index (LOI) needed by membrane combustion is determined. The specific result is listed in Table 1.
Table 2 Limit oxygen index test
Sample name LOI/% Combustion time /s
Embodiment 1 23.10 32
Embodiment 2 26.00 36
Comparative Example 1 18.70 24
Comparative Example 2 19.40 24
[68] Seen from Table 2, the LOI of the electrolyte membranes (embodiments 1 and 2) with the black phosphorene added is increased compared with the electrolyte membrane (comparative example 1) with no black phosphorene added and increased along with increase of the adding quantity of the black phosphorene, and the LOI of the embodiment 2 is increased by 10% to the maximum degree; and by comparing the embodiment 2 with the comparative example 2, adding of the black phosphorene in the comparative example 2 omitting deaerating operation barely plays a role mainly because of oxidation of the black phosphorene under the same black phosphorene adding quantity, and it can be seen that the deaerating step is very important.
[69] In description of the specification, description of reference terms such as ‘one embodiment’, ‘example’ and ‘specific example’ refers that specific features, structures, materials or characteristics described with reference to the embodiment or example are contained in at least one embodiment or example of the disclosure. In the specification, schematic representation for the above terms does not necessarily refer to the same embodiments or examples. Moreover, the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a proper manner.
[70] The preferred embodiments of the disclosure disclosed above are only used for helping illustrate the disclosure. The preferred embodiments do not narrate all details in detail, but do not limit the disclosure, and are only specific implementations. Obviously, many modifications and changes can be made according to the content of the specification. The specification selects and specifically describes these embodiments in order to better explain the principle and actual application of the disclosure so that those skilled in the art can better understand and utilize the disclosure. The disclosure is only limited by claims and all scopes and equivalents thereof.
Claims (6)
1. A preparation method of a flame-retardant all-solid-state battery electrolyte membrane, characterized in that the preparation method comprises the following steps: S1: selecting black phosphorus, and putting the black phosphorus in an organic solvent for ultrasonic smashing and centrifugation after the black phosphorus is subjected to electrochemical assisting method treatment to obtain a dispersion of a flame-retardant material; S2: adding the dispersion in S1 into PEO-based electrolyte powder, performing constant- temperature stirring, and fully dissolving the materials to obtain a polymer solution; and S3: pouring the polymer solution prepared in S2 into an electrolyte membrane forming mold, and sequentially putting the mold in a deaerating plant and a vacuum drying box to be dried to prepare an electrolyte membrane.
2. The preparation method according to claim 1, characterized in that an electrochemical assisting method comprises the following steps: (1) weighing 0.01-0.1 g of black phosphorus as an anode, taking a platinum net as a counter electrode, and assembling the black phosphorus, the platinum net and electrolyte into an electrolytic tank; and (2) reacting at the voltage of 3-10 V.
3. The preparation method according to claim 1, characterized in that the mass of the flame-retardant material in S1 accounts for 0.03%0-0.06%o that of the organic solvent; and the organic solvent is one of DMF and NMP; time and frequency of ultrasonic smashing are 80-120 min and 20-33 Hz respectively; and speed and time of centrifugation are 3000-8000 r/min and 10-20 min respectively.
4. The preparation method according to claim 1, characterized in that the mass of the PEO- based electrolyte powder in S2 accounts for 6%-12% that of the polymer solution; the PEO-based electrolyte powder is prepared by mixing PEO, PVDE, Al,O; and LiTFSI in a certain ratio; and a fully-dissolving method comprises the following steps: stirring for 4-6 h at constant temperature of 50-70 degrees Celsius and stirring speed of 50-200 r/min.
5. The preparation method according to claim 1, characterized in that a drying method in S3 comprises the following steps: putting the mold in the deaerating plant to be dried for 3-8 h at constant temperature of 50-70 degrees Celsius, and then putting the mold in the vacuum drying box to be dried for 3-6 h at constant temperature of 30-60 degrees Celsius.
BL-5429 LU501569
6. Application of the electrolyte membrane prepared through the preparation method of the flame-retardant all-solid-state battery electrolyte membrane according to any one of claims 1-5 in the technical field of lithtum ion battery solid-state electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU501569A LU501569B1 (en) | 2022-03-01 | 2022-03-01 | Preparation method of flame-retardant all-solid-state battery electrolyte membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU501569A LU501569B1 (en) | 2022-03-01 | 2022-03-01 | Preparation method of flame-retardant all-solid-state battery electrolyte membrane |
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| Publication Number | Publication Date |
|---|---|
| LU501569B1 true LU501569B1 (en) | 2023-09-06 |
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| LU501569A LU501569B1 (en) | 2022-03-01 | 2022-03-01 | Preparation method of flame-retardant all-solid-state battery electrolyte membrane |
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| Country | Link |
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| LU (1) | LU501569B1 (en) |
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2022
- 2022-03-01 LU LU501569A patent/LU501569B1/en active IP Right Grant
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