CN117747935A - Gel polymer electrolyte, lithium metal battery and preparation method and application thereof - Google Patents
Gel polymer electrolyte, lithium metal battery and preparation method and application thereof Download PDFInfo
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- CN117747935A CN117747935A CN202311783490.2A CN202311783490A CN117747935A CN 117747935 A CN117747935 A CN 117747935A CN 202311783490 A CN202311783490 A CN 202311783490A CN 117747935 A CN117747935 A CN 117747935A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- -1 diphenyl azide phosphate Chemical compound 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 239000004305 biphenyl Substances 0.000 claims abstract description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
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- 229920002239 polyacrylonitrile Polymers 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 6
- SORGEQQSQGNZFI-UHFFFAOYSA-N [azido(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(N=[N+]=[N-])OC1=CC=CC=C1 SORGEQQSQGNZFI-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010041 electrostatic spinning Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a gel polymer electrolyte, a lithium metal battery and a preparation method and application thereof, wherein the gel polymer electrolyte comprises a framework and a precursor solution, the framework comprises a polymer spinning film, the precursor solution comprises a polymerization monomer, an initiator and an electrolyte, and the polymerization monomer comprises diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate; the gel polymer electrolyte obtained by in-situ polymerization and the electrode have good interface performance by selecting diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate to be matched as a polymerization monomer and taking a polymer spinning film as a framework, so that a lithium metal battery prepared from the gel polymer electrolyte has higher ion conductivity and excellent multiplying power performance and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a gel polymer electrolyte, a lithium metal battery, and a preparation method and application thereof.
Background
The lithium metal battery is used as a novel chemical power supply, has the advantages of high energy density, environmental friendliness, no memory effect and the like, and has been widely applied to products such as notebook computers, digital cameras, mobile phones, various new energy automobiles and the like in recent years.
At present, the commonly used electrolyte is liquid electrolyte adopting a carbonic ester solvent, and on one hand, the liquid electrolyte can generate side reaction in the process of charging and discharging the battery to generate byproducts influencing the performance of the battery; on the other hand, the liquid electrolyte has the risk of leakage, and the battery has the risks of combustion and explosion due to the combination of the properties of easy volatilization, flammability and the like of the electrolyte. To reduce or even eliminate these risks, gel Polymer Electrolytes (GPEs) have been developed that have a simple preparation process, relatively high ionic conductivity, flexibility and safety, and have great potential for use in lithium metal batteries, as compared to liquid electrolytes.
However, conventional polymer electrolytes are typically synthesized using ex-situ polymerization methods, which can result in poor contact between the electrode and the electrolyte and impair cell performance. For example CN110603681a discloses a composition for gel polymer electrolytes comprising: an oligomer; an anionic stabilizing additive; a polymerization initiator; a lithium salt; and a nonaqueous organic solvent, and also relates to a gel polymer electrolyte prepared by using the composition, and a lithium secondary battery prepared by using the gel polymer electrolyte.
Therefore, how to improve the synthesis method of the gel polymer electrolyte to reduce the interface stability between the electrode and the electrolyte and to develop the energy density advantage of the lithium metal battery has become the key point of current research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a gel polymer electrolyte, a lithium metal battery and a preparation method and application thereof, wherein the gel polymer electrolyte uses diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate as polymerization monomers in a matching way, and uses a polymer spinning film as a framework, so that the gel polymer electrolyte and an electrode obtained by in-situ polymerization have good interface performance, and the lithium metal battery prepared from the gel polymer electrolyte has higher ion conductivity, excellent multiplying power performance and cycle performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a gel polymer electrolyte comprising a backbone and a precursor solution;
the skeleton comprises a polymer spinning film, and the precursor solution comprises a polymerization monomer, an initiator and an electrolyte; the polymeric monomers include diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate.
According to the gel polymer electrolyte provided by the invention, the polymer spinning membrane is taken as a framework, and the polymerization monomer, the initiator and the electrolyte are taken as precursor solutions, when the gel polymer electrolyte is used, the precursor solutions are added into the framework and then put into the battery core together, the gel polymer electrolyte is directly polymerized in the battery core, the gel polymer electrolyte obtained by in-situ polymerization has good interface performance with the electrode, and the advantage of high energy density of the lithium metal battery can be fully exerted, so that the lithium metal battery containing the gel polymer electrolyte has higher ion conductivity, excellent rate performance and cycle performance;
specifically, the DPPA is rich in terminal hydroxyl groups and polyunsaturated c=c double bonds, which can be cross-linked and polymerized with TFOA to form a cross-linked fluoropolymer that forms an interpenetrating network between nanofibers in a polymer spinning film, thereby obtaining the gel polymer electrolyte; according to the invention, DPPA and TFOA are further preferably selected to be matched as a polymerization monomer, so that the interface performance of a gel polymer electrolyte obtained by subsequent polymerization and an electrode can be further improved, and the cycle performance and the rate capability of a lithium metal battery are further improved; further, in one aspect, the terminal hydroxyl groups of the DPPA are effective to inhibit polymer crystallization, providing more amorphous regions, thereby improving the local mobility of the polymer chains and improving ionic conductivity; and the oxygen atom of the DPPA molecular chain and the nitrile group of polyacrylonitrile can jointly construct a high-efficiency Li+ transmission channel, which is beneficial to the high-efficiency migration of Li+; on the other hand, the long-chain structure of the TFOA not only inhibits the crystallization of the polymer, but also is beneficial to forming a stable SEI film rich in LiF on a lithium metal anode, thereby effectively promoting the uniform deposition/stripping of lithium metal and reducing the growth of lithium dendrites so as to prolong the cycle life of a lithium metal battery.
Preferably, the polymer spinning membrane comprises a polyacrylonitrile spinning membrane, and the polyacrylonitrile spinning membrane not only has good oxidation resistance, but also can improve the mechanical property of gel polymer electrolyte, and the combination between polymers obtained after different monomers are polymerized is more uniform, so that the cycle performance of the battery is more favorably improved.
Preferably, the polymer spinning film has a thickness of 9 to 10 μm, for example, 9.1 μm, 9.2 μm, 9.3 μm, 9.4 μm, 9.5 μm, 9.6 μm, 9.7 μm, 9.8 μm or 9.9 μm, etc.
Preferably, the polymer fibers in the polymer spinning film have a diameter of 150 to 200nm, for example 160nm, 170nm, 180nm or 190nm, etc.
Preferably, the polymer spinning film is prepared by electrospinning.
Preferably, the method for electrostatic spinning specifically comprises the following steps: and (3) dissolving the polymer in an organic solvent, then carrying out electrostatic spinning, and drying to remove the organic solvent to obtain the polymer spinning film.
Preferably, the mass ratio of diphenyl azide phosphate to 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate is (1-5): 1, e.g., 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, etc.
Preferably, the initiator is used in an amount of 0.5 to 1%, for example 0.6%, 0.7%, 0.8% or 0.9%, etc., based on 100% by mass of the polymerized monomer.
Preferably, the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, or dimethyl azobisisobutyrate.
Preferably, the electrolyte is 90 to 100% by mass, for example 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% by mass, based on 100% by mass of the polymer monomer.
Preferably, the lithium salt of the electrolyte comprises lithium bis (trifluoromethanesulfonyl) imide and/or lithium bis (fluorosulfonyl) imide.
Preferably, the solvent of the electrolyte comprises any one or a combination of at least two of ethylene carbonate, diethyl carbonate or dimethyl carbonate.
Preferably, the content of lithium salt in the electrolyte is 0.9 to 1mol/L, for example 0.91mol/L, 0.93mol/L, 0.95mol/L, 0.97mol/L, 0.99mol/L, or the like.
Preferably, the gel polymer electrolyte is obtained by adding the precursor solution to the skeleton and performing in-situ polymerization.
Preferably, the volume of the skeleton is 4cm 3 The precursor solution is added in an amount of 80 to 150. Mu.L, for example, 60. Mu.L, 70. Mu.L, 80. Mu.L, 90. Mu.L, 100. Mu.L, 110. Mu.L, 120. Mu.L, 130. Mu.L, 140. Mu.L, or the like.
In the present invention, if the backbone is selected to be a circular polymer spinning film, the diameter of the circular polymer spinning film is about 19mm.
In a second aspect, the present invention provides a lithium metal battery comprising a gel polymer electrolyte as described in the first aspect.
Preferably, the lithium metal battery further comprises a shell, a positive plate, a negative plate and a diaphragm.
In a third aspect, the present invention provides a method for preparing a lithium metal battery according to the second aspect, the method comprising: adding the precursor solution of the gel polymer electrolyte according to the first aspect into a framework, then placing the framework into an electric core, and heating to obtain the lithium metal battery.
Preferably, the heating is preceded by the further step of aging at room temperature, which aids in allowing the precursor solution to sufficiently infiltrate the electrode and polymer spinning membrane.
Preferably, the heating temperature is 55 to 65 ℃, for example 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, or the like.
Preferably, the heating time is 10 to 13 hours, for example 10.3 hours, 10.6 hours, 10.9 hours, 11 hours, 11.5 hours, 12 hours or 12.5 hours, etc.
In a fourth aspect, the invention provides an application of the lithium metal battery in a new energy automobile.
Compared with the prior art, the invention has the following beneficial effects:
the gel polymer electrolyte provided by the invention comprises a framework and a precursor solution, wherein the framework comprises a polymer spinning film, the precursor solution comprises a polymerization monomer, an initiator and an electrolyte, and the polymerization monomer comprises diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate; the gel polymer electrolyte obtained by in-situ polymerization and the electrode have good interface performance by selecting diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate as polymerization monomers and taking a polymer spinning film as a framework, so that a lithium metal battery containing the gel polymer electrolyte has higher ion conductivity (up to 1.4-2.3 mS/cm), excellent rate capability (the capacity retention rate of 1C/0.2C is up to 75-85%) and cycle performance (the capacity retention rate of 100 circles at normal temperature 0.2C is up to 83-91%).
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The materials and equipment involved in the embodiments of the present invention, unless specifically stated, may be commercially available or prepared according to existing methods;
wherein, the TCGG liquid adopted is as follows: lithium hexafluorophosphate (LiPF) comprising 1M 6 ) And a volume ratio of 1:1 of ethylene carbonate to ethylene carbonate.
Diphenyl azide phosphate: DPPA;
3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate: TFOA;
polyacrylonitrile: a PAN;
dimethylformamide: DNF;
nickel cobalt lithium manganate 811: NCM811.
Example 1
A gel polymer electrolyte, the preparation method comprising the steps of:
(1) Adding PAN into DMF to obtain 10wt% PAN spinning solution, stirring at room temperature for 12h to obtain stable and uniform high-pressure spinning state, then carrying out electrostatic spinning, vacuum drying the obtained PAN film at 80 ℃ for 12h, completely removing DMF solvent, and finally cutting the PAN film into wafers to obtain PAN electrostatic spinning film with the overall diameter of 19mm, the thickness of 9.5 mu m and the straightness of PAN fiber of about 180nm; wherein, the electrostatic spinning parameters are as follows: the applied voltage was 22kV, the needle diameter was 21G, the air gap distance was 18cm, the drum collection speed was 300 revolutions per minute, the needle movement speed was 30 mm per second, and the spinning distance was solution flow rate=0.8 mL/h;
weighing DPPA and TFOA according to a mass ratio of 3:1, adding 1wt% of AIBN and 95wt% of TCGG electrolyte (based on DPPA and TFOA), and continuously stirring for 1h at 30 ℃ to completely dissolve the mixture to obtain a precursor solution (DPPA-TFOA-TCGG);
(2) Adding 120 mu L of DPPA-TFOA-TCGG precursor solution into the PAN electrostatic spinning film, putting the precursor solution into an electric core together, and aging the assembled electric core for 3 hours at room temperature to ensure that the DPPA-TFOA-TCGG can fully wet the electrode and the PAN electrostatic spinning film; and finally, heating the battery cell in an oven at 60 ℃ for 12 hours, and completing in-situ polymerization of the monomer to obtain the gel polymer electrolyte.
Example 2
A gel polymer electrolyte was distinguished from example 1 in that the mass ratio of DPPA and TFOA was 2:1, and other raw materials and preparation methods were the same as those of example 1.
Example 3
A gel polymer electrolyte was distinguished from example 1 in that the mass ratio of DPPA and TFOA was 4:1, and the other raw materials and the preparation method were the same as those of example 1.
Example 4
A gel polymer electrolyte was distinguished from example 1 in that the mass ratio of DPPA and TFOA was 0.5:1, and other raw materials and preparation methods were the same as those of example 1.
Example 5
A gel polymer electrolyte was distinguished from example 1 in that the mass ratio of DPPA and TFOA was 6:1, and other raw materials and preparation methods were the same as those of example 1.
Example 6
A gel polymer electrolyte was distinguished from example 1 in that the DPPA-TFOA-TCGG precursor solution was added in an amount of 80. Mu.L in step (2), and the other raw materials and the preparation method were the same as those of example 1.
Example 7
A gel polymer electrolyte was distinguished from example 1 in that the DPPA-TFOA-TCGG precursor solution was added in an amount of 150. Mu.L in step (2), and the other raw materials and the preparation method were the same as those of example 1.
Example 8
A gel polymer electrolyte was distinguished from example 1 in that the DPPA-TFOA-TCGG precursor solution was added in an amount of 60. Mu.L in step (2), and the other raw materials and the preparation method were the same as those of example 1.
Example 9
A gel polymer electrolyte was distinguished from example 1 in that the DPPA-TFOA-TCGG precursor solution was added in an amount of 200. Mu.L in step (2), and the other raw materials and the preparation method were the same as those of example 1.
Comparative example 1
A gel polymer electrolyte, the preparation method comprising the steps of:
(1) Weighing DPPA and TFOA according to a mass ratio of 3:1, adding 1wt% of AIBN and 95wt% of TCGG electrolyte (based on DPPA and TFOA), and continuously stirring for 1h at 30 ℃ to completely dissolve the mixture to obtain a precursor solution (DPPA-TFOA-TCGG);
(2) Adding 120 mu L of DPPA-TFOA-TCGG precursor solution into the battery core, and aging the assembled battery core for 3 hours at room temperature to ensure that the DPPA-TFOA-TCGG can fully wet the electrode and the PAN electrostatic spinning film; and finally, heating the battery cell in an oven at 60 ℃ for 12 hours, and completing in-situ polymerization of the monomer to obtain the gel polymer electrolyte.
Comparative example 2
A gel polymer electrolyte was different from example 1 in that TFOA was not added, and other raw materials and preparation methods were the same as those of example 1.
Comparative example 3
A gel polymer electrolyte was distinguished from example 1 in that DPPA was not added, and other raw materials and preparation methods were the same as those of example 1.
Performance test:
1. preparation of the battery cell: the preparation flow of the cells in examples 1 to 9 and comparative examples 1 to 3 is as follows:
(1) Taking commercial NCM811 as a positive electrode active material, weighing three substances according to the mass ratio of positive electrode active material to conductive agent (super-p) to polyvinylidene fluoride (PVDF) =8:1:1, mixing the three substances in solvent N-methylpyrrolidone (NMP), and uniformly stirring to obtain positive electrode slurry (the solid content is 60%); coating the positive electrode slurry on an aluminum foil, and vacuum drying for 12 hours at 90 ℃ to obtain a positive electrode plate;
(2) Taking a metal lithium sheet as a negative electrode, taking the positive electrode sheet obtained in the step (1) as a positive electrode, and assembling a CR2032 button cell in a glove box filled with Ar gas by using the in-situ synthesized gel polymer electrolyte of the invention as a PE diaphragm, wherein H 2 O and O 2 The content of the polymer is kept below 0.1ppm, and the battery cell is obtained.
2. Electrochemical performance test:
(1) Ion conductivity: the cells finally obtained in examples 1 to 9 and comparative examples 1 to 3 were subjected to an ion conductivity test (frequency range 10) on an electrochemical workstation (ZIVE SP 1) 6 0.1Hz, temperature 25 ℃), the conductivity is calculated according to the formula σ=l/R/S, where L is the thickness of the gel polymer electrolyte layer, R is the bulk resistance, and S is the electrode/electrolyte contact area;
(2) Cycle performance and rate performance: at room temperature, the electrochemical performance test is carried out by adopting a LAND CT2001A battery test system, the cycle performance test is carried out according to 0.2C/0.2C, the multiplying power performance test is carried out according to 1C/0.2C, and the test voltage range is 3-4.3V.
The results of the above performance tests are shown in table 1 below:
TABLE 1
From the data in table 1, it can be seen that:
the ionic conductivity of the lithium metal batteries prepared from the gel polymer electrolytes provided in examples 1 to 9 is 0.9 to 2.5mS/cm, the rate capability test shows that the capacity retention rate of 1C/0.2C is up to 60 to 85 percent, and the cycle capability test shows that the capacity retention rate of 0.2C/0.2C is up to 72 to 91 percent;
compared with example 1, the gel polymer electrolyte provided in comparative example 1 is not provided with a skeleton, resulting in lower ionic conductivity after the battery is fabricated and poorer cycle performance and rate performance; the gel polymer electrolytes provided in comparative example 2 and comparative example 3 each use only a single polymer monomer, and also resulted in poor rate performance and cycle performance after the battery was fabricated, and greatly reduced ionic conductivity.
The applicant states that the present invention is illustrated by the above examples as a gel polymer electrolyte, a lithium metal battery, and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A gel polymer electrolyte, characterized in that the gel polymer electrolyte comprises a backbone and a precursor solution;
the skeleton comprises a polymer spinning film, and the precursor solution comprises a polymerization monomer, an initiator and an electrolyte; the polymeric monomers include diphenyl azide phosphate and 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate.
2. The gel polymer electrolyte of claim 1 wherein the polymer spinning membrane comprises a polyacrylonitrile spinning membrane;
preferably, the thickness of the polymer spinning film is 9-10 μm;
preferably, the diameter of the polymer fiber in the polymer spinning film is 150-200 nm;
preferably, the polymer spinning film is prepared by electrospinning.
3. The gel polymer electrolyte according to claim 1 or 2, wherein the mass ratio of the diphenyl azide phosphate to 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl acrylate is (1 to 5): 1;
preferably, the initiator is used in an amount of 0.5 to 1% based on 100% by mass of the polymerized monomer;
preferably, the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, or dimethyl azobisisobutyrate.
4. A gel polymer electrolyte according to any one of claims 1 to 3, wherein the electrolyte is used in an amount of 90 to 100% based on 100% by mass of the polymer monomer;
preferably, the lithium salt of the electrolyte comprises lithium bis (trifluoromethanesulfonyl) imide and/or lithium bis (fluorosulfonyl) imide;
preferably, the solvent of the electrolyte comprises any one or a combination of at least two of ethylene carbonate, diethyl carbonate or dimethyl carbonate;
preferably, the molar concentration of lithium salt in the electrolyte is 0.9 to 1mol/L.
5. The gel polymer electrolyte according to any one of claims 1 to 4, wherein the gel polymer electrolyte is obtained by adding the precursor solution to the skeleton and then polymerizing in situ;
preferably, the volume of the skeleton is 4cm 3 The addition amount of the precursor solution is 80-150 mu L.
6. A lithium metal battery comprising the gel polymer electrolyte of any one of claims 1 to 5.
7. The lithium metal battery of claim 6, further comprising a housing, a positive electrode sheet, a negative electrode sheet, and a separator.
8. A method of preparing the lithium metal battery of claim 6 or 7, comprising: the precursor solution of the gel polymer electrolyte according to any one of claims 1 to 5 is added into a framework, and then the framework is put into an electric core, and the lithium metal battery is obtained after heating.
9. The method of claim 8, wherein the step of aging is further comprised at room temperature prior to heating;
preferably, the heating temperature is 55-65 ℃;
preferably, the heating time is 10 to 13 hours.
10. Use of a lithium metal battery according to claim 6 or 7 in a new energy vehicle.
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