CN115863745A - Polymer/graphene composite solid electrolyte membrane and preparation method thereof - Google Patents
Polymer/graphene composite solid electrolyte membrane and preparation method thereof Download PDFInfo
- Publication number
- CN115863745A CN115863745A CN202210219452.3A CN202210219452A CN115863745A CN 115863745 A CN115863745 A CN 115863745A CN 202210219452 A CN202210219452 A CN 202210219452A CN 115863745 A CN115863745 A CN 115863745A
- Authority
- CN
- China
- Prior art keywords
- polymer
- lithium
- solid electrolyte
- electrolyte membrane
- graphene
- 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.)
- Granted
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000001723 curing Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 150000002641 lithium Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 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 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Images
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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention relates to H01M, in particular to a polymer/graphene composite solid electrolyte membrane and a preparation method thereof. The method comprises the following steps: and adding the lithium-loaded graphene into the pre-complex, mixing, curing and drying to obtain the solid electrolyte membrane. The invention provides a solid electrolyte membrane, wherein lithium-loaded graphene is added into a polymer-lithium salt complex system, so that the obtained polymer/graphene composite material can effectively improve the crystallization phenomenon of polymer PEO and the growth of lithium dendrite in the charging and discharging process, the electrochemical window and the charging and discharging specific capacity are obviously improved, the solid electrolyte membrane has better charging and discharging multiplying power and cycle performance, and the impedance is effectively reduced. In addition, the method provided by the invention can effectively reduce the problems of uneven distribution of graphene and long-time heating and mixing in the preparation process, reduce energy consumption and provide the solid electrolyte membrane with stronger interaction between the graphene and the polymer-lithium salt and higher lithium ion transmission rate.
Description
Technical Field
The invention relates to H01M, in particular to a polymer/graphene composite solid electrolyte membrane and a preparation method thereof.
Background
The solid polymer electrolyte is also called as an ion conductive polymer and is mainly obtained by complexing the polymer and metal salt, wherein the polymer mainly comprises PEO, PAN, PMMA, PVC and the like, and the PEO has better flexibility because of containing a-C-O-C-structure capable of complexing with the metal salt, and is widely applied to the solid polymer electrolyte.
However, in a PEO-metal salt, such as a lithium salt complex electrolyte system, because PEO has high crystallinity, the PEO consists of an amorphous region, a pure PEO crystalline region and a salt-rich region at normal temperature, wherein the crystalline region does not participate in ion conduction, and only the amorphous region participates, so that the PEO ionic conductivity at normal temperature is only 10 -6 S·cm -1 And about it, affect its electrical properties.
CN112786957A provides a polymer solid electrolyte, a preparation method thereof and a polymer solid battery. The cycling stability of the battery is improved by coating the graphene material on the surface of the solid electrolyte, but when the battery is used for a long time in a coating mode, powder falling, lithium dendrite and the like can be caused along with the volume effect, and the long-term use is influenced.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a polymer/graphene composite solid electrolyte membrane, comprising:
(1) Adding a polymer and a lithium salt into a solvent, and mixing to obtain a pre-complex;
(2) Adding lithium-loaded graphene into a pre-complex, and mixing to obtain a suspension;
(3) And solidifying and drying the suspension to obtain the solid electrolyte membrane.
As a preferable technical scheme of the invention, the weight ratio of the polymer to the lithium salt is 13-17: 1, as 13: 1. 14: 1. 15: 1. 16: 1. 17:1.
as a preferred technical scheme of the invention, the polymer is selected from at least one of PEO, PAN, PMMA, PVC, PVDF and PPO. Preferably, the PEO has a weight average molecular weight of 500000 to 800000, such as 500000, 600000, 700000, 800000.
As one aspect of the present inventionIn a preferred embodiment, the lithium salt is selected from lithium perchlorate (LiClO) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium dioxalate borate (LiBOB), lithium trifluoromethanesulfonate (CF) 3 LiO 3 S) and lithium bis (fluorosulfonyl) imide (LiFSI).
As a preferable technical scheme of the invention, the mixing time in the step (1) is more than or equal to 5 hours, and the invention does not specifically limit the mixing time in the step (1) and only needs to obtain a uniform polymer solution.
In a preferred embodiment of the present invention, the solvent is at least one selected from nitrile solvents, ketone solvents, alcohol solvents, ether solvents, and amine solvents, preferably nitrile solvents, amine solvents, such as acetonitrile and DMF.
As a preferred technical solution of the present invention, the weight ratio of the polymer to the solvent is 1:3 to 6.
In the mixing process of the polymer and the lithium salt, the inventor finds that by controlling the type and molecular weight of the polymer, the PEO with high flexibility and proper molecular weight is used, the rate of the PEO with proper molecular weight extending and dissolving in the solvent is utilized, the PEO with proper molecular weight is continuously complexed with the lithium salt in the solvent, the formation of a uniform organic C-O-C-inorganic lithium salt double-complexing system is favorably promoted, and the ionic structure formed after complexing further expands the contact space between the PEO and the solvent, so that the PEO and the lithium salt are promoted to be more quickly formed into uniform polymer solution with proper viscosity, and the combination and dispersion of subsequent lithium-loaded graphene are promoted.
As a preferable technical scheme of the invention, the weight ratio of the polymer to the lithium-loaded graphene is 8-10: 1, as 8: 1. 8.5: 1. 9: 1. 9.5: 1. 10:1. the lithium-carrying group of lithium in the lithium-carrying graphene can be a sulfonate, a nitrate, and the like, and is not particularly limited.
As a preferable technical solution of the present invention, in the lithium-loaded graphene, a molar ratio of C to S is 12 to 5:1, as 12: 1. 11: 1. 10:1. 9: 1. 8: 1. 7:1. 6: 1. 5:1.
as a preferred technical solution of the present invention, in the lithium-loaded graphene, the molar ratio of Li to S is 1:2 to 4, such as 1:2. 1:2.2, 1:2.5, 1:2.8, 1:3. 1:3.2, 1:3.5, 1:3.8, 1:4.
the inventor finds that the concentration of sulfonate and lithium ions on the surface of graphene is controlled by adding lithium graphene into a pre-complex and controlling the proportion of C to S, li to S, so that a stable charge layer is formed with flexible PEO, the transfer of the lithium ions is promoted, the intermolecular acting force of a solid electrolyte membrane is improved, the volume change in the charge-discharge process is reduced, the problem of lithium dendrite and the like caused by the fact that the lithium ions form a continuous channel is avoided, the reduction of impedance and the improvement of charge-discharge multiplying power are promoted, and the cycle electrical property is promoted.
As a preferred technical scheme of the present invention, the lithium-loaded graphene is further modified by organic silicon, and includes: adding lithium-loaded graphene into water to obtain a lithium-loaded graphene dispersion solution, adding organic silicon, mixing at 70-90 ℃ for 1-3 h, drying at 120-140 ℃, and sintering at high temperature to obtain the modified lithium-loaded graphene.
As a preferable technical scheme, the weight ratio of the organic silicon to the lithium-loaded graphene is 0.1-0.2: 1. as a preferable technical scheme of the invention, the organic silicon is amino organic silicon and carboxyl organic silicon, and the weight ratio of the amino organic silicon to the carboxyl organic silicon is 1:0.4 to 0.6.
As a preferred embodiment of the present invention, the viscosity of the amino silicone is 2000 to 4000cSt, such as OFX-8040A (viscosity 3000 cSt) from Dow Corning.
As a preferred embodiment of the present invention, the carboxyl silicone has a viscosity of 2000 to 4000cSt, such as BY16-880 (viscosity of 2500 cSt) BY Dow Corning.
In addition, the inventors also found that when the lithium-loaded graphene is added to the pre-complex, partial agglomeration occurs due to strong pi-pi action between the graphene, and a uniform suspension is difficult to form, and the inventors found that when the modified lithium-loaded graphene is used, the carboxyl action of the amino organosilicon and the carboxyl graphene and the action between the amino organosilicon and the carboxyl organosilicon are utilized, so that organosilicon chains with different lengths are formed on the surface of the graphene, when the modified lithium-loaded graphene enters the pre-complex with certain viscosity, the pre-complex can be promoted to be dispersed in a pre-complex solution, the mixing time is shortened, meanwhile, the organosilicon chains with different lengths can be crossed with PEO to a certain extent, a crystallization area in an electrolyte is further reduced, the occurrence of ion conduction is promoted, meanwhile, the graphene with different thicknesses is prevented from moving in a subsequent drying process, a structure with uniform gaps is formed, and the improvement of conductivity and cycle performance is promoted.
As a preferable technical scheme of the invention, the stirring time is 8-16 h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and 16h.
In the preferable technical scheme of the invention, in the step (3), during the solidification and drying of the suspension, the suspension is dried at normal temperature and then heated and dried.
As a preferable technical scheme of the invention, the time for drying at normal temperature is more than 20h, such as 20h, 22h, 24h, 26h and 28h.
As a preferred technical scheme of the invention, the time of the heating and drying is more than 10 hours, and the temperature of the heating and drying is 50-65 ℃, such as 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃ and 65 ℃.
In addition, the inventor also finds that in the process of curing and drying, after drying for a period of time at normal temperature, heating and drying are carried out, the interface contact between the lithium-loaded graphene and a PEO-lithium salt complex system can be further promoted, the movement of PEO and an organic silicon chain is promoted, and a more complete and compact graphene-lithium salt-PEO inorganic-organic lithium ion exchange structure is formed, so that when the lithium ion exchange structure is used for a battery, the problems of powder falling and the like are reduced while the lithium ion transmission efficiency is improved, the contact area with an electrode is promoted, and a battery material with a higher electrochemical window and a higher charge-discharge multiplying power is obtained.
The second aspect of the invention provides a polymer/graphene composite solid electrolyte membrane prepared by the preparation method of the polymer/graphene composite solid electrolyte membrane.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a solid electrolyte membrane, wherein lithium-loaded graphene is added into a polymer-lithium salt complex system, so that the obtained polymer/graphene composite material can effectively improve the crystallization phenomenon of polymer PEO and the growth of lithium dendrite in the charging and discharging process, the electrochemical window and the charging and discharging specific capacity are obviously improved, the solid electrolyte membrane has better charging and discharging multiplying power and cycle performance, and the impedance is effectively reduced. In addition, the method provided by the invention can effectively reduce the problems of uneven distribution of graphene and long-time heating and mixing in the preparation process, reduce energy consumption and provide the solid electrolyte membrane with stronger interaction between the graphene and the polymer-lithium salt and higher lithium ion transmission rate.
Drawings
Fig. 1 is a graph showing the first charge-discharge characteristics and cycle characteristics of a solid electrolyte of comparative example 1 (left in fig. 1) and example 1 (right in fig. 1).
Detailed Description
Examples
Example 1
The present embodiment provides a method for preparing a polymer/graphene composite solid electrolyte membrane, including:
(1) PEO (weight average molecular weight 60 ten thousand) and LiClO 4 According to the PEO: li weight ratio =16: and 5, stirring for more than 5 hours by using a magnetic stirrer to obtain a uniform polymer solution.
(2) According to the weight ratio of PEO: adding sulfonic acid lithium-loaded graphene =9:1 into the obtained solution, and stirring for 12 hours to obtain a black homogeneous suspension; in the sulfonic acid lithium-loaded graphene, the molar ratio of C to S is 10:1, the molar ratio of Li to S is 1:3.
(3) And pouring the suspension into a polytetrafluoroethylene mold, drying the suspension in a glove box for more than 24h at room temperature, drying the electrolyte membrane in a vacuum drying box at 60 ℃ for more than 12h, and finally punching and cutting the membrane into a wafer with the diameter of 16mm to obtain the PEO/lithium-loaded graphene composite solid electrolyte membrane.
Example 2
The present embodiment provides a method for preparing a polymer/graphene composite solid electrolyte membrane, including:
(1) PEO (weight average molecular weight 60 ten thousand) and LiClO 4 According to the PEO: li weight ratio =16: and 5, stirring for more than 5 hours by using a magnetic stirrer to obtain a uniform polymer solution.
(2) According to the weight ratio of PEO: adding the modified sulfonic acid lithium-loaded graphene =9:1 into the obtained solution, and stirring for 8 hours to obtain a black homogeneous suspension; the preparation method of the modified sulfonic acid lithium-loaded graphene comprises the following steps: adding sulfonic acid lithium-loaded graphene into water to obtain a lithium-loaded graphene dispersion solution, adding organic silicon, mixing at 90 ℃ for 2h, drying at 120 ℃, and sintering at high temperature to obtain the modified lithium-loaded graphene. In the sulfonic acid lithium-loaded graphene, the molar ratio of C to S is 10:1, the molar ratio of Li to S is 1:3, the weight ratio of the organic silicon to the lithium-loaded graphene is 0.15:1, the organic silicon is amino organic silicon OFX-8040A and carboxyl organic silicon BY16-880, and the weight ratio is 1:0.5.
(3) And pouring the suspension into a polytetrafluoroethylene mold, drying the suspension in a glove box at room temperature for more than 24h, drying the electrolyte membrane in a vacuum drying box at 60 ℃ for more than 12h, and finally punching and cutting the membrane into a wafer with the diameter of 16mm to obtain the PEO/lithium-loaded graphene composite solid electrolyte membrane.
Comparative example 1
This example provides a method for producing a polymer solid electrolyte membrane, comprising:
(1) PEO (weight average molecular weight 60 ten thousand) and LiClO 4 According to the PEO: li weight ratio =16: and 5, stirring the mixture for more than 5 hours by using a magnetic stirrer to obtain a uniform polymer solution.
(3) And pouring the polymer solution into a polytetrafluoroethylene mold, drying the polymer solution in a glove box for more than 24 hours at room temperature, drying the electrolyte membrane in a vacuum drying box at 60 ℃ for more than 12 hours, and finally punching and cutting the membrane into a wafer with the diameter of 16mm to obtain the PEO/lithium-loaded graphene composite solid electrolyte membrane.
Evaluation of Properties
The electrolyte membranes provided in examples and comparative examples were fabricated into cells in the order of positive electrode-electrolyte membrane-negative electrode, and subjected to tab mounting and wrapping to obtain lithium batteries for the following tests.
1. Electrochemical window: the electrolyte membranes provided in examples and comparative examples were subjected to electrochemical window tests by linear sweep voltammetry, and it was found that examples 1 and 2 have a wider electrochemical window, in which example 1 is improved by 0.9V compared to comparative example 1, and example 2 is improved by 1V compared to comparative example 1.
2. Impedance: the electrolyte membranes provided in examples and comparative examples were subjected to EIS testing for ac impedance before cycling and ac impedance after 100 cycles, and it was found that the impedance of example 1 was reduced by 2k Ω before cycling and 3k Ω after cycling compared to comparative example 1, and that the impedance of example 2 was reduced by 2.2k Ω before cycling and 3.1k Ω after cycling compared to comparative example 1.
3. And (3) charge and discharge test: the electrolyte membranes provided by the examples and the comparative examples are respectively charged and discharged, and it is found that the specific charge capacities of 0.1C and 1C of the example 1 are respectively increased by 15mAh/g and 19mAh/g, the specific discharge capacities are respectively increased by 14mAh/g and 23mAh/g, and the specific charge capacities of 0.1C and 1C of the example 1 are respectively increased by 18mAh/g and 21mAh/g, and the specific discharge capacities are respectively increased by 14mAh/g and 25mAh/g, compared with the comparative example 1.
4. Long cycle life performance: the electrolyte membranes provided in the examples and comparative examples were subjected to cycle tests, respectively, and as shown in fig. 1, it was found that the specific discharge capacity of the battery of comparative example 1 decayed very rapidly, and after 30 cycles, the specific discharge capacity was almost 0, indicating that the cycle performance was unstable. Although the specific discharge capacity of the battery in the embodiment 1 is attenuated, the specific discharge capacity is still 77mAh/g after 30 circles, the cycle performance is still stable after 100 circles of cycle, and the specific discharge capacity is still 59mAh/g. Therefore, the polymer/graphene composite solid electrolyte membrane provided by the invention has better cycle stability. The specific capacity retention rate (99.8%) of the battery using the polymer/graphene composite solid electrolyte membrane after 30 cycles is higher than the specific capacity retention rate (44.1%) of the battery using the PEO solid electrolyte membrane.
Claims (10)
1. A preparation method of a polymer/graphene composite solid electrolyte membrane is characterized by comprising the following steps:
(1) Adding a polymer and a lithium salt into a solvent, and mixing to obtain a pre-complex;
(2) Adding lithium-loaded graphene into a pre-complex, and mixing to obtain a suspension;
(3) And solidifying and drying the suspension to obtain the solid electrolyte membrane.
2. The method for producing a polymer/graphene composite solid electrolyte membrane according to claim 1, wherein the weight ratio of the polymer to the lithium salt is 13 to 17:1.
3. the method for producing a polymer/graphene composite solid electrolyte membrane according to claim 1, wherein the polymer is selected from at least one of PEO, PAN, PMMA, PVC, PVDF, and PPO.
4. The method of preparing a polymer/graphene composite solid electrolyte membrane according to claim 3, wherein the PEO has a weight average molecular weight of 500000 to 800000.
5. The method for producing a polymer/graphene composite solid electrolyte membrane according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium dioxalate borate, lithium trifluoromethanesulfonate, and lithium bistrifluorosulfonylimide.
6. The method for producing a polymer/graphene composite solid electrolyte membrane according to claim 1, wherein the weight ratio of the polymer to the lithium-loaded graphene is 8 to 10:1.
7. the method for producing a polymer/graphene composite solid electrolyte membrane according to claim 6, wherein the molar ratio of C to S in the lithium-loaded graphene is 12 to 5:1.
8. the method for producing a polymer/graphene composite solid electrolyte membrane according to claim 6, wherein in the lithium-loaded graphene, the molar ratio of Li to S is 1:2 to 4.
9. The method for producing a polymer/graphene composite solid electrolyte membrane according to any one of claims 1 to 8, wherein the lithium-loaded graphene is further modified with silicone.
10. A polymer/graphene composite solid electrolyte membrane prepared by the method for preparing a polymer/graphene composite solid electrolyte membrane according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219452.3A CN115863745B (en) | 2022-03-08 | 2022-03-08 | Polymer/graphene composite solid electrolyte membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219452.3A CN115863745B (en) | 2022-03-08 | 2022-03-08 | Polymer/graphene composite solid electrolyte membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115863745A true CN115863745A (en) | 2023-03-28 |
| CN115863745B CN115863745B (en) | 2023-11-14 |
Family
ID=85660009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210219452.3A Active CN115863745B (en) | 2022-03-08 | 2022-03-08 | Polymer/graphene composite solid electrolyte membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115863745B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120134164A (en) * | 2011-05-31 | 2012-12-12 | 경희대학교 산학협력단 | Polymer composite electrolyte membranes and preparation method thereof |
| KR20150026088A (en) * | 2013-08-30 | 2015-03-11 | 전남대학교산학협력단 | Polymer electrolyte composite membrane, method for fabricating the smae and energy storage device comprising the same |
| CN105218992A (en) * | 2015-07-08 | 2016-01-06 | 苏州高通新材料科技有限公司 | Sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application |
| CN105366644A (en) * | 2015-10-09 | 2016-03-02 | 苏州高通新材料科技有限公司 | Sulfonated graphene metal salt and preparation method and application thereof |
| CN108346819A (en) * | 2018-02-09 | 2018-07-31 | 徐鸿翔 | A kind of high energy solid state battery and preparation method thereof |
| CN108417888A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of no lithium salts modified graphene composite solid electrolyte material, dielectric film and preparation method thereof |
| CN109722165A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | Modified graphene/sulfur-containing organosilicon composite anti-corrosive liquid, coating, preparation method and application |
| CN110172157A (en) * | 2018-08-01 | 2019-08-27 | 江苏华夏制漆科技有限公司 | A kind of modified organic silicone resin and its preparation method and application |
| CN111029515A (en) * | 2019-12-25 | 2020-04-17 | 中国地质大学（武汉） | Sulfonated graphene oxide-based single-ion polymer electrolyte membrane and preparation method and application thereof |
| JP2020066557A (en) * | 2018-10-25 | 2020-04-30 | 国立研究開発法人理化学研究所 | Sulfo group-containing graphene oxide, solid polymer electrolyte membrane, membrane electrode assembly, and method for manufacturing solid polymer fuel cell |
| CN113265185A (en) * | 2021-05-24 | 2021-08-17 | 广州市上善纳米材料有限公司 | Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof |
-
2022
- 2022-03-08 CN CN202210219452.3A patent/CN115863745B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120134164A (en) * | 2011-05-31 | 2012-12-12 | 경희대학교 산학협력단 | Polymer composite electrolyte membranes and preparation method thereof |
| KR20150026088A (en) * | 2013-08-30 | 2015-03-11 | 전남대학교산학협력단 | Polymer electrolyte composite membrane, method for fabricating the smae and energy storage device comprising the same |
| CN105218992A (en) * | 2015-07-08 | 2016-01-06 | 苏州高通新材料科技有限公司 | Sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application |
| CN105366644A (en) * | 2015-10-09 | 2016-03-02 | 苏州高通新材料科技有限公司 | Sulfonated graphene metal salt and preparation method and application thereof |
| CN109722165A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | Modified graphene/sulfur-containing organosilicon composite anti-corrosive liquid, coating, preparation method and application |
| CN108346819A (en) * | 2018-02-09 | 2018-07-31 | 徐鸿翔 | A kind of high energy solid state battery and preparation method thereof |
| CN108417888A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of no lithium salts modified graphene composite solid electrolyte material, dielectric film and preparation method thereof |
| CN110172157A (en) * | 2018-08-01 | 2019-08-27 | 江苏华夏制漆科技有限公司 | A kind of modified organic silicone resin and its preparation method and application |
| JP2020066557A (en) * | 2018-10-25 | 2020-04-30 | 国立研究開発法人理化学研究所 | Sulfo group-containing graphene oxide, solid polymer electrolyte membrane, membrane electrode assembly, and method for manufacturing solid polymer fuel cell |
| CN111029515A (en) * | 2019-12-25 | 2020-04-17 | 中国地质大学（武汉） | Sulfonated graphene oxide-based single-ion polymer electrolyte membrane and preparation method and application thereof |
| CN113265185A (en) * | 2021-05-24 | 2021-08-17 | 广州市上善纳米材料有限公司 | Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115863745B (en) | 2023-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Balo et al. | Flexible gel polymer electrolyte based on ionic liquid EMIMTFSI for rechargeable battery application | |
| US10243236B2 (en) | Overcharging preventive electrolyte and lithium-ion battery | |
| CN102414902B (en) | Electrolyte for electrochemical device, electrolyte solution using same, and nonaqueous electrolyte battery | |
| WO2013185629A1 (en) | High energy density charge and discharge lithium battery | |
| JP2023158083A (en) | lithium ion capacitor | |
| CN103500845A (en) | Cross-linked polymer-based all-solid-state electrolyte material and application of cross-linked polyoxyethylene ether | |
| CN104838533A (en) | Nonaqueous electrolyte secondary battery and method for manufacturing same | |
| CN105308778A (en) | Electricity-storage-device electrode, manufacturing method therefor, and electricity-storage device using said electrode | |
| JP2001057234A (en) | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery | |
| KR100387393B1 (en) | Composite polymer electrolyte containing room-temperature molten salt | |
| JP2001057235A (en) | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery | |
| JP5167566B2 (en) | Non-aqueous electrolyte for lithium secondary battery | |
| CN117219850A (en) | Electrolyte and battery | |
| CN109119687A (en) | electrolyte and electrochemical energy storage device | |
| CN111834663A (en) | Semi-solid/solid battery prepared by electrochemical oxidation-reduction method and method | |
| CN110752404B (en) | Electrolyte, battery containing electrolyte and electric vehicle | |
| CN115863745B (en) | Polymer/graphene composite solid electrolyte membrane and preparation method thereof | |
| CN115312867A (en) | High-performance low-temperature electrolyte and application thereof in lithium/sodium ion battery | |
| CN113206292B (en) | Polymer-based composite solid electrolyte and preparation method and application thereof | |
| CN104813517A (en) | Electricity storage device, electrode used therein, and porous sheet | |
| CN113140800B (en) | Preparation method of lithium ion battery electrolyte and secondary battery containing electrolyte | |
| KR102539971B1 (en) | Solid Electrolyte Composition, Preparation Method thereof, and Battery Comprising the Same | |
| JP4076738B2 (en) | Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery | |
| CN109671978B (en) | High-voltage-resistant solid polymer electrolyte, preparation method and application thereof | |
| CN115995598A (en) | Multifunctional sodium battery electrolyte additive and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |