CN117199515A - Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution - Google Patents
Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution Download PDFInfo
- Publication number
- CN117199515A CN117199515A CN202311046400.1A CN202311046400A CN117199515A CN 117199515 A CN117199515 A CN 117199515A CN 202311046400 A CN202311046400 A CN 202311046400A CN 117199515 A CN117199515 A CN 117199515A
- Authority
- CN
- China
- Prior art keywords
- precursor solution
- lithium
- electrolyte
- porous
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 43
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 lithium trifluoromethanesulfonyl imide Chemical class 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000007774 positive electrode material Substances 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IWYGQFVCGINTMU-UHFFFAOYSA-N C1(=CC=C(N)C=C1)C1=CC=C(N)C=C1.N1C=NC=C1 Chemical compound C1(=CC=C(N)C=C1)C1=CC=C(N)C=C1.N1C=NC=C1 IWYGQFVCGINTMU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
The invention relates to a precursor solution of an in-situ polyelectrolyte, comprising: an electrolyte, a polymer monomer, and an initiator; the electrolyte comprises: an organic solvent and a lithium salt; the organic solvent is selected from: at least one of ethylene carbonate, methyl ethyl carbonate or fluoroethylene carbonate; the molar concentration of the lithium salt in the electrolyte is 1mol/L-2.6mol/L, and the lithium salt is selected from the following: at least one of lithium trifluoromethanesulfonyl imide, lithium bisoxalato borate, lithium hexafluorophosphate or lithium tetrafluoroborate; the mass concentration of the polymer monomer in the precursor solution is 3% -10%; the mass concentration of the initiator in the precursor solution is 0.5% -2% of the mass of the polymer monomer. The electrolyte is prepared by adopting a precursor solution in-situ polymerization method, so that leakage of electrolyte can be effectively avoided, generation of lithium dendrite is inhibited, room-temperature ionic conductivity is ensured, meanwhile, a certain mechanical strength is given to the electrolyte, an electrolyte electrochemical window is improved, and a high-voltage positive electrode material can be better matched to obtain a lithium ion battery with high energy density.
Description
Technical Field
The invention relates to the field of solid-state batteries, in particular to a precursor solution of an in-situ polyelectrolyte and a solid-state battery prepared from the precursor solution.
Background
Lithium ion batteries have been widely used in various fields such as intelligent electronic devices, electric vehicles, smart grids, and the like. The continuous development of electric equipment now puts higher and higher requirements on high-performance and high-safety lithium ion batteries, and the improvement of the energy density of the lithium ion batteries is still the focus of research at present.
In general, the search for electrode materials with higher energy densities and increasing the loading of existing electrode materials are effective methods of increasing the energy density of a battery. The current commercial lithium battery prepares the active material into electrode slurry, coats the electrode slurry on a current collector, and prepares the electrode by removing the solvent. The design and use of thick electrodes is one of the methods for achieving high energy output of medium-cell batteries, and the increase in electrode thickness means an increase in the content of electrode active materials, thereby achieving high capacity and high energy density of electrode materials. However, a compromise between electrode thickness and electrode performance is required during electrode design. The greater the thickness of the electrode, the greater the ion transport distance in the cell and the greater the resistance, resulting in lower specific capacity and discharge voltage. In addition, if the electrode thickness is too thick, the N-methylpyrrolidone (NMP) removal process may cause a change in the internal microstructure of the electrode, damaging the electrochemical performance of the electrode, and thus the electrode active material loading is limited to the electrode thickness (about 70 μm as in conventional standard electrode thickness). The continuous pore structure and long-range conductive network inside the thick electrode are key to design high-performance thick electrodes.
Meanwhile, the safety of lithium ion batteries is also a non-negligible problem in research. The liquid electrolyte in the traditional lithium ion battery has the safety problems of easy liquid leakage, short circuit, easy solvent volatilization and the like, the instability of the liquid electrolyte under high pressure also easily leads to the reduction of the battery performance, the liquid electrolyte is difficult to match with a high-pressure positive electrode material, and the solid electrolyte becomes a hot spot of research in recent years due to the characteristics of high safety, wide electrochemical window, good processability and the like. The gel electrolyte has the characteristics of solid and liquid, has certain cohesiveness and mechanical strength, and can ensure good ion diffusion transmission efficiency.
The invention prepares the flexible self-supporting porous thick electrode by a non-solvent induced phase precipitation method, achieves higher active material loading capacity, and prepares the solid-state battery with high energy density. The solid-state battery adopts an in-situ polymerization mode, a precursor solution of the gel solid electrolyte is simultaneously permeated into the porous positive electrode plate, the porous electrolyte membrane and the porous negative electrode plate, and then thermal polymerization curing is carried out, and the porous positive electrode plate, the porous electrolyte membrane and the porous negative electrode plate are integrated through the gel solid electrolyte, so that the interface contact performance of the electrode and the electrolyte can be effectively improved.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a precursor solution of an in-situ polyelectrolyte and a solid-state battery prepared from the precursor solution.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a first aspect of the present invention provides a precursor solution for an in situ polyelectrolyte, comprising: an electrolyte, a polymer monomer, and an initiator; wherein,
the electrolyte comprises: an organic solvent and a lithium salt;
the organic solvent is selected from the group consisting of: at least one of ethylene carbonate, methyl ethyl carbonate or fluoroethylene carbonate;
the molar concentration of the lithium salt in the electrolyte is 1mol/L-2.6mol/L, and the lithium salt is selected from the group consisting of: at least one of lithium trifluoromethanesulfonyl imide, lithium bisoxalato borate, lithium hexafluorophosphate or lithium tetrafluoroborate;
the mass concentration of the polymer monomer in the precursor solution is 3% -10%;
the mass concentration of the initiator in the precursor solution is 0.5% -2% of the mass of the polymer monomer.
Preferably, the organic solvent is ethylene carbonate, methyl ethyl carbonate and fluoroethylene carbonate, and the volume ratio of the ethylene carbonate, the methyl ethyl carbonate and the fluoroethylene carbonate is 1:1:1.
Preferably, the organic solvent is ethylene carbonate and methyl ethyl carbonate, and the volume ratio of the ethylene carbonate to the methyl ethyl carbonate is 2:3.
Preferably, the lithium salt is lithium trifluoromethanesulfonyl imide and lithium bisoxalato borate, and the molar ratio of the lithium trifluoromethanesulfonyl imide to the lithium bisoxalato borate is 3:2.
Preferably, the lithium salt is lithium hexafluorophosphate.
Preferably, the polymer monomer is at least one of N, N' -methylenebisacrylamide or ethylene glycol dimethacrylate.
Preferably, the initiator is azobisisobutyronitrile.
Preferably, the mass concentration of the initiator in the precursor solution is 0.5% of the mass of the polymer monomer.
A second aspect of the present invention provides a method for manufacturing a solid-state battery, comprising the steps of:
s1, sequentially preparing a porous positive electrode plate, a porous electrolyte membrane and a porous negative electrode plate;
s2, preparing a precursor solution as described above;
s3, soaking and wetting the porous positive electrode plate, the porous electrolyte membrane and the porous negative electrode plate in the precursor solution, assembling the porous positive electrode plate, the porous electrolyte membrane and the porous positive electrode plate in the sequence of a negative electrode shell, the porous negative electrode plate, the porous electrolyte membrane and the positive electrode shell, sealing, and standing for 4-6 h at 60-80 ℃ to obtain the solid-state battery.
Preferably, the preparation method of the porous positive electrode plate comprises the following steps: dissolving a positive electrode active material, conductive carbon black and a binder in a proper amount of N-methyl pyrrolidone; coating the surface of the clean aluminum foil by a scraper; and after standing at room temperature, transferring the mixture into an isopropanol sedimentation tank, after sedimentation is completed, transferring the mixture into a blast drying oven, drying the mixture, stamping the mixture by a sheet cutting machine, transferring the stamped mixture into a vacuum oven, and drying the stamped mixture to obtain the porous positive electrode sheet.
Preferably, the preparation method of the porous electrolyte membrane includes: dissolving active ceramic electrolyte powder LATP and a polymer matrix in N-methyl pyrrolidone, uniformly stirring, adding isopropanol, and continuously and uniformly stirring; coating the surface of the clean substrate by a scraper; and standing at room temperature, transferring into a drying oven, drying in a vacuum drying oven, and obtaining the porous electrolyte membrane.
Preferably, the preparation method of the porous negative electrode plate comprises the following steps: dissolving a cathode active material, conductive carbon black and a binder in a proper amount of N-methyl pyrrolidone; coating the surface of the clean copper foil by a scraper; and after standing at room temperature, transferring the mixture to a deionized water sedimentation tank, transferring the mixture to a blast drying box after complete sedimentation, drying the mixture, stamping the mixture by a cutting machine, transferring the stamped mixture to a vacuum oven, and drying the stamped mixture to obtain the porous negative electrode plate.
Preferably, 50. Mu.L to 100. Mu.L of the precursor solution is also added during assembly.
A third aspect of the present invention is to provide a solid-state battery manufactured by the manufacturing method as described above.
Compared with the prior art, the invention has the following technical effects:
the electrolyte is prepared by adopting a precursor solution in-situ polymerization method, so that leakage of electrolyte can be effectively avoided, generation of lithium dendrite is inhibited, room-temperature ionic conductivity is ensured, a certain mechanical strength is given to the electrolyte, an electrolyte electrochemical window is improved, and a high-voltage positive electrode material can be better matched to obtain a lithium ion battery with high energy density; the porous positive electrode plate, the porous electrolyte membrane and the porous negative electrode plate are of continuous porous structures, and the electrolyte after in-situ polymerization connects the three to realize integration, so that the contact between the electrolyte and electrode active substances is increased, and the interface resistance between the electrolyte and the electrode is effectively reduced.
Drawings
Fig. 1 is a schematic view of a process for manufacturing a solid-state battery according to the present invention;
wherein, the reference numerals include:
a precursor solution 1 of an in situ polyelectrolyte; a porous positive electrode sheet 2; a porous electrolyte membrane 3; and a porous negative electrode plate 4.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting.
Example 1
The embodiment provides a solid-state battery and a preparation method thereof, wherein the preparation method comprises the following steps:
s1-1, preparing ternary polymerization polyimide: 3.20g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB), 2.24g of 2- (4-aminophenyl) -5-aminobenzene imidazole (BIA) and 6.44g of 3,3', 4' -benzophenone carboxylic acid dianhydride (BTDA) are weighed out in sequence as monomers, dissolved in sufficient N-methylpyrrolidone (NMP) and a soluble ternary copolyimide (PI) is synthesized in one step under nitrogen atmosphere and at high temperature, wherein the molar ratio of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl to 2- (4-aminophenyl) -5-aminobenzene imidazole in the ternary copolyimide is 1:1, a step of;
s1-2, preparing a porous positive plate 2: the positive electrode active material is 622-type nickel-cobalt-manganese ternary positive electrode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The adhesive is ternary polymerization polyimide and polyvinylidene fluoride (PVDF), and the mass concentration of the ternary polymerization polyimide in the adhesive is 30%; sequentially weighing an anode active material, conductive carbon black and a binder, wherein the mass ratio of the anode active material to the conductive carbon black to the binder is 88:5:7, dissolving in a proper amount of N-methyl pyrrolidone; coating the aluminum foil on the clean surface of the aluminum foil by a scraper, wherein the coating thickness is 500 mu m; standing at room temperature for 5min, transferring to an isopropanol sedimentation tank, transferring to a forced air drying oven after 60min sedimentation is completed, drying at 80 ℃ for 2h, stamping by a sheet cutting machine to obtain a round positive pole piece with the diameter of 10mm, transferring to a vacuum oven, drying at 110 ℃ for 12h to fully remove water and release deformation stress, transferring to a glove box, and weighing for later use;
s1-3, preparing a porous electrolyte membrane 3: dissolving active ceramic electrolyte powder LATP and a polymer matrix (ternary polymerization polyimide and polyvinylidene fluoride) in N-methyl pyrrolidone, stirring uniformly, adding isopropanol, continuously stirring uniformly, wherein the total mass concentration of LATP in the mixture is 5%, the total mass concentration of ternary polymerization polyimide in the mixture is 2%, the total mass concentration of polyvinylidene fluoride in the mixture is 8%, and the total mass concentration of isopropanol in the mixture is 10%; coating the surface of the clean substrate by a scraper, wherein the coating thickness is 100 mu m; standing at room temperature for 10min, transferring to a baking oven, heating at 50deg.C for 1h, heating at 80deg.C for 1h, drying the obtained porous electrolyte membrane 3 in a vacuum baking oven for 12h, and transferring to a glove box for use;
s1-4, preparing a porous negative electrode plate 4: the negative electrode active material is graphite; the adhesive is ternary polymerization polyimide and polyvinylidene fluoride (PVDF), and the mass concentration of the ternary polymerization polyimide in the adhesive is 30%; sequentially weighing a negative electrode active material, conductive carbon black and a binder, wherein the mass ratio of the negative electrode active material to the conductive carbon black to the binder is 87:5:8, dissolving in a proper amount of N-methyl pyrrolidone; coating the surface of the clean copper foil by a scraper, wherein the coating thickness is 200 mu m; standing at room temperature for 5min, transferring to a deionized water sedimentation tank, transferring to a forced air drying oven after 60min sedimentation is completed, drying at 80 ℃ for 2h, stamping by a sheet cutting machine to obtain a round negative electrode sheet with the diameter of 12mm, transferring to a vacuum oven, drying at 80 ℃ for 12h to fully remove water and release deformation stress, transferring to a glove box, and weighing for later use;
s2, preparing a precursor solution 1 of an in-situ polyelectrolyte: the organic solvent is Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and fluoroethylene carbonate (FEC), and the volume ratio of ethylene carbonate, ethylmethyl carbonate and fluoroethylene carbonate is 1:1:1; the lithium salt is lithium trifluoromethanesulfonyl imide (LiTFSi) and lithium bisoxalato borate (LiBOB), the molar ratio of the lithium trifluoromethanesulfonyl imide to the lithium bisoxalato borate is 3:2, and the molar concentration of the lithium salt in the electrolyte is 1mol/L; adding a polymer monomer (N, N ' -methylene bisacrylamide) and an initiator (azodiisobutyronitrile, AIBN) into the electrolyte, wherein the mass concentration of the N, N ' -methylene bisacrylamide in a precursor solution is 3 percent, and the mass concentration of the azodiisobutyronitrile in the precursor solution is 0.5 percent of the mass of the N, N ' -methylene bisacrylamide; after uniform mixing, a precursor solution 1 of the in-situ polyelectrolyte is obtained;
s3, after soaking and wetting the porous positive electrode plate 2, the porous electrolyte membrane 3 and the porous negative electrode plate 4 in the precursor solution, assembling the negative electrode shell, the porous negative electrode plate 4, the porous electrolyte membrane 3, the porous positive electrode plate 2 and the positive electrode shell in sequence, and adding 50-100 mu L of the precursor solution during assembling; sealing and standing for 4 hours at 60 ℃ to obtain the solid-state battery.
Detection example 1
The porous positive electrode sheet 2 and the porous negative electrode sheet 4 in example 1 were replaced with stainless Steel Sheets (SS) or/and lithium sheets (Li), and SS/GPE/SS, SS/GPE/Li, and Li/GPE/Li (positive electrode/electrolyte/negative electrode) were prepared, respectively, SS/GPE/SS was used for testing ion conductivity, SS/GPE/Li was used for testing cyclic voltammetry, and Li/GPE/Li was used for testing lithium ion transfer number.
Example 2
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 1 in that:
in step S1-3, the total mass concentration of the ternary polymerization polyimide is 4%.
Example 3
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 2 in that:
in step S2, the mass concentration of N, N' -methylenebisacrylamide in the precursor solution is 5%.
Example 4
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 3 in that:
in the step S1-4, the anode active material is a silicon-carbon composite material, and the mass ratio of the anode active material, the conductive carbon black and the binder is 87:5:8.
example 5
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 4 in that:
in step S2, the lithium salt is lithium hexafluorophosphate.
Example 6
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 5 in that:
in the step S2, the organic solvent is methyl ethyl carbonate and methyl ethyl carbonate, and the volume ratio of the methyl ethyl carbonate to the methyl ethyl carbonate is 2:3.
example 7
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 6 in that:
in step S2, the molar concentration of the lithium salt in the electrolyte was 2.5mol/L.
Example 8
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 7 in that:
in step S2, the polymer monomer is ethylene glycol dimethacrylate.
Example 9
This example provides another solid-state battery and a method of manufacturing the same, which is different from example 8 in that:
in the step S1-2, after the positive electrode active material, the conductive carbon black and the binder are dissolved in a proper amount of N-methyl pyrrolidone, the mixture is coated on the surface of a clean glass plate through a scraper;
in the step S1-4, the binder is (polyvinylidene fluoride-hexafluoropropylene) copolymer (PVDF-HFP), and the negative electrode active material, the conductive carbon black and the binder are dissolved in a proper amount of N-methyl pyrrolidone and then coated on the surface of a clean glass plate through a scraper.
Comparative example
This comparative example provides a liquid battery and a method for manufacturing the same, which is different from example 1 in that:
in step S2, no polymer monomer and no initiator are added.
Test examples 2 to 10
Test examples 2-10 the corresponding performance data of examples 2-9 and comparative example, respectively, were tested in the same manner as test example 1, and therefore will not be described in detail.
TABLE 1 Performance data detection results
In summary, the electrolyte is prepared by adopting the precursor solution in-situ polymerization method, so that leakage of the electrolyte can be effectively avoided, generation of lithium dendrites is inhibited, room-temperature ionic conductivity is ensured, meanwhile, certain mechanical strength is given to the electrolyte, an electrolyte electrochemical window is improved, and a high-voltage positive electrode material can be better matched to obtain a lithium ion battery with high energy density; the porous positive electrode plate 2, the porous electrolyte membrane 3 and the porous negative electrode plate 4 are all of continuous porous structures, and electrolyte after in-situ polymerization connects the three to realize integration, so that the contact between the electrolyte and electrode active substances is increased, and the interface resistance between the electrolyte and the electrode is effectively reduced.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, and it will be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the description and illustrations of the present invention, and are intended to be included within the scope of the present invention.
Claims (10)
1. A precursor solution of an in-situ polyelectrolyte, which is characterized by comprising an electrolyte, a polymer monomer and an initiator; wherein the electrolyte comprises an organic solvent and lithium salt;
the organic solvent is at least one selected from ethylene carbonate, methyl ethyl carbonate or fluoroethylene carbonate;
the molar concentration of the lithium salt in the electrolyte is 1mol/L-2.6mol/L, and the lithium salt is selected from the group consisting of: at least one of lithium trifluoromethanesulfonyl imide, lithium bisoxalato borate, lithium hexafluorophosphate or lithium tetrafluoroborate;
the mass concentration of the polymer monomer in the precursor solution is 3% -10%;
the mass concentration of the initiator in the precursor solution is 0.5% -2% of the mass of the polymer monomer.
2. The precursor solution of claim 1, wherein the organic solvent is ethylene carbonate, ethylmethyl carbonate, and fluoroethylene carbonate, the volume ratio of ethylene carbonate, ethylmethyl carbonate, and fluoroethylene carbonate being 1:1:1; or the organic solvent is ethylene carbonate and methyl ethyl carbonate, and the volume ratio of the ethylene carbonate to the methyl ethyl carbonate is 2:3.
3. The precursor solution of claim 1, wherein the lithium salt is lithium trifluoromethanesulfonyl imide and lithium bis (oxalato) borate, and wherein the molar ratio of lithium trifluoromethanesulfonyl imide to lithium bis (oxalato) borate is 3:2.
4. The precursor solution of claim 1, wherein the lithium salt is lithium hexafluorophosphate.
5. The precursor solution of claim 1, wherein the polymer monomer is at least one of N, N-methylenebisacrylamide or ethylene glycol dimethacrylate.
6. The precursor solution of claim 5 wherein the initiator is azobisisobutyronitrile.
7. The precursor solution of claim 6, wherein the mass concentration of the initiator in the precursor solution is 0.5% of the mass of the polymer monomer.
8. A method of manufacturing a solid-state battery, comprising the steps of:
s1, sequentially preparing a porous positive electrode plate, a porous electrolyte membrane and a porous negative electrode plate;
s2, preparing the precursor solution as claimed in any one of claims 1 to 7;
s3, soaking and wetting the porous positive electrode plate, the porous electrolyte membrane and the porous negative electrode plate in the precursor solution, assembling the porous positive electrode plate, the porous electrolyte membrane and the porous positive electrode plate in the sequence of a negative electrode shell, the porous negative electrode plate, the porous electrolyte membrane and the positive electrode shell, sealing, and standing for 4-6 h at 60-80 ℃ to obtain the solid-state battery.
9. The method of claim 8, wherein 50 μl to 100 μl of the precursor solution is further added during assembly.
10. A solid-state battery produced by the production method according to any one of claims 8 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311046400.1A CN117199515A (en) | 2023-08-18 | 2023-08-18 | Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311046400.1A CN117199515A (en) | 2023-08-18 | 2023-08-18 | Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117199515A true CN117199515A (en) | 2023-12-08 |
Family
ID=88996996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311046400.1A Pending CN117199515A (en) | 2023-08-18 | 2023-08-18 | Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117199515A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118054063A (en) * | 2024-03-04 | 2024-05-17 | 深圳欣界能源科技有限公司 | Electrolyte prepolymerization solution, preparation method thereof, solid electrolyte and application |
-
2023
- 2023-08-18 CN CN202311046400.1A patent/CN117199515A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118054063A (en) * | 2024-03-04 | 2024-05-17 | 深圳欣界能源科技有限公司 | Electrolyte prepolymerization solution, preparation method thereof, solid electrolyte and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110085904B (en) | Flexible composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof | |
| EP2648265A1 (en) | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same | |
| CN111430788A (en) | Composite solid electrolyte membrane, preparation method and solid lithium battery | |
| CN111697262A (en) | Composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof | |
| CN111725468B (en) | Silicon dioxide inorganic nanoparticle reinforced polyolefin diaphragm and application thereof | |
| CN106654365A (en) | Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof | |
| CN111200128B (en) | Preparation method of positive electrode material for inhibiting transition metal ions in positive electrode material of lithium ion battery from dissolving out | |
| CN114976263B (en) | Positive electrode and electrolyte integrated solid-state battery and preparation method thereof | |
| CN114171788B (en) | Sandwich type solid composite electrolyte membrane and preparation method and application thereof | |
| CN114335700A (en) | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method | |
| CN110459723A (en) | Battery diaphragm, preparation method thereof and battery with battery diaphragm | |
| CN112670450A (en) | Negative pole piece for solid-state battery and preparation method and application thereof | |
| CN114335701A (en) | Composite solid electrolyte membrane and preparation method thereof | |
| CN110676433A (en) | Composite lithium cathode, preparation method thereof and lithium battery | |
| CN114069037A (en) | Gel polymer electrolyte, preparation method and application thereof, solid-state lithium battery and preparation method thereof | |
| CN116845346A (en) | In-situ polymerization double-crosslinking polymer electrolyte and preparation method and application thereof | |
| CN117199515A (en) | Precursor solution of in-situ polyelectrolyte and solid-state battery prepared from precursor solution | |
| CN111799508B (en) | All-solid-state polymer electrolyte diaphragm, preparation method and all-solid-state lithium ion battery | |
| CN114388745A (en) | High-performance lithium ion battery self-supporting polymer thick pole piece and preparation method thereof | |
| CN114512708A (en) | Preparation method and application of lithium ion composite solid electrolyte | |
| CN110970654B (en) | Composite gel polymer electrolyte for lithium ion battery and preparation and application thereof | |
| CN113285119B (en) | PVDF standard solid electrolyte of lithium ion battery and preparation method thereof | |
| CN115224359A (en) | Polymer electrolyte, preparation method thereof and lithium ion all-solid-state battery | |
| CN113540693A (en) | Lithium battery separator | |
| CN113363573A (en) | Preparation method of solid electrolyte, solid electrolyte and all-solid-state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |