CN112421104A - Elastomer epoxy resin-based all-solid-state electrolyte and preparation method and application thereof - Google Patents
Elastomer epoxy resin-based all-solid-state electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an elastomer epoxy resin-based all-solid-state electrolyte, a preparation method and application thereof, which solve the technical problems that impurities are introduced into the existing crosslinked solid-state polymer electrolyte in the preparation process, a solvent is used, and the working temperature range of the existing thermoplastic polymer solid-state electrolyte is narrow; the alkali metal salt is dissociated into alkali metal cations by solvation of the epoxy resin monomer with the curing agent; the epoxy resin monomer and the curing agent are subjected to a crosslinking reaction, and the obtained electrolyte is an elastomer electrolyte self-supporting membrane which is used as a framework of the electrolyte and is responsible for ion transmission. The invention also provides a preparation method and application thereof. The invention can be used in the field of lithium ion battery solid electrolyte.
Description
Technical Field
The invention relates to a solid electrolyte of a lithium ion battery, in particular to an elastomer epoxy resin-based all-solid electrolyte and a preparation method and application thereof.
Background
With the development of lithium batteries, intelligent electronic devices and electric vehicles have been developed and upgraded, and people have begun to explore lithium secondary batteries with higher energy density. Lithium metal is an ideal choice for lithium battery anodes due to its high energy density and low reduction potential. However, conventional lithium batteries generally employ organic liquid electrolytes, which tend to react poorly with lithium metal, thereby limiting the use of lithium metal anodes. Moreover, the reports of explosion of mobile phones, computers and automobile power devices are frequent in the news, and the research on batteries with high safety performance is not easy from the safety perspective. The traditional liquid electrolyte has the defects of leakage, high volatility, flammability, explosiveness and the like, so that an electrolyte providing safety guarantee is urgently needed.
Solid polymer is used as electrolyte with development prospect, and has the advantages of relatively light weight, low reactivity with electrodes, good high and low temperature performance, easy molding, relatively low cost and the like. The solid electrolyte can be divided into gel electrolyte, quasi-solid electrolyte and all-solid electrolyte, and the addition content of the electrolyte is gradually reduced to no addition. The appearance of the all-solid electrolyte on the source head solves the safety problem that the organic electrolyte is inflammable and explosive due to leakage.
Nowadays, a variety of polymer matrices, such as Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF) and polyethylene oxide (PEO), have been studied and applied to solid polymer electrolytes. Among them, PEO is the most widely used polymer electrolyte matrix due to its superior complexing ability. However, the low ionic conductivity of PEO-based electrolytes at room temperature limits their use as commercial electrolytes. Since PEO crystallizes at room temperature and the crystalline segment cannot move freely, i.e., in an inelastic state, preventing the transport of lithium ions, PEO electrolytes exhibit lower conductivity at room temperature. On one hand, the content of lithium salt is increased by adding a solvent or the ionic conductivity is increased by adding a plasticizer, and the definition of the full solid electrolyte state is not pure due to the residue of the solvent. On the other hand, the all-solid-state electrolyte matrix of the thermoplastic polymer represented by PEO has a lower melting point, which limits the working temperature range of the battery, and thus unstable potential safety hazards such as electrolyte leakage and the like still occur under high-temperature conditions. To overcome these problems, many people adopt various methods to form PEO molecules into a crosslinked network-like elastic state, thereby inhibiting crystallization and improving toughness. However, the crosslinking reaction currently used is generally initiated by thermal radicals, such as benzoyl peroxide, azobisisobutyronitrile, and the like. The disadvantage is the formation of by-products, such as free radicals and residual monomers. The reactivity of the byproducts and lithium metal is extremely high, and the performance of the battery is seriously influenced. Some people use inorganic nano-particle doping (chem.Sus.chem,2019,12(20): 4708-.
Then, the epoxy resin as a thermosetting material has the advantages of no melting point limitation, no crosslinking of a curing agent, designability and the like, and is regarded by the field of solid electrolyte. Epoxy resins were first applied to a framework material in an electrolyte because of their excellent mechanical properties. Researchers have attempted to modify PEO by utilizing an interpenetrating network of epoxy resin with PEO, where the epoxy resin network serves as a backbone primarily to provide mechanical properties. (proceedings of Guizhou university of Industrial science 1997(3):70-74.) Taiwan university of success, team of Kucazulene, 2003Epoxy resin PEGDE and polyetheramine (D400 and D2000) are matched with LiClO4The cross-linked network all-solid-state electrolyte is successfully prepared, and unfortunately, the highest ionic conductivity at 25 ℃ is only 10 due to no good lithium salt selection and preparation method-7The system could not be applied to full cells up to 2020 on the S/cm scale. (Polymer,2003,44(10):2957-2964.) the optical epitaxy problem group uses epoxy resin PEGDGE to catalyze the ring-opening polymerization of epoxy groups by the decomposition and hydrolysis of lithium salt LiDFOB, thereby obtaining Polymer electrolytes, although they can obtain self-supporting electrolyte membranes only by designing cellulose supporting membranes, they cannot become epoxy resin-based all-solid-state electrolytes in the true sense due to the fragile crosslinking network, but this is an extraordinary attempt. (adv.sci.2017,4,1700174.) next, the league group of sienna university introduced the concept of epoxy resin in solid electrolyte, which utilizes the double bond addition reaction of glycidyl methacrylate and oligo (ethylene oxide) methyl ether methacrylic acid to synthesize polymer electrolyte, but since epoxy groups are contained only in the polymer, curing and crosslinking cannot be performed by using epoxy groups, it cannot be really called epoxy resin-based all-solid electrolyte. (Electrochimica Acta, Vol.318,302-313,2019.) Choi, U.Hyeok team crosslinking epoxy resin DGEBA as a matrix and methyl tetrahydrophthalic anhydride as a crosslinking agent into a network electrolyte system and improving the conductivity to 10- 4S/cm, which increases the proportion of plasticizer, results in systems which can only be referred to as quasi-solid electrolytes and are not all-solid systems. (Macromolecular Research,2018,26.5:459--7The S/cm level has two methods for improving the performance. One is the addition of a silicone plasticizer and an organic solvent PC with a plasticizing effect, although the ionic conductivity of the process is raised to 10 at room temperature-3S/cm, but the lithium salt content is only 5.7 wt%, so that the conductivity is improved to an upper limit, and the electrolyte is complicatedThe system and the process operation difficulty are increased. In addition, the incomplete removal of the solvent and the appearance of the plasticizer enable the solid electrolyte material not to be crosslinked, and the potential safety hazard of the electrolyte in a non-elastomer state still exists. (Solid State Ionics,2018,326: 150-. In addition, the existence of the ionic liquid component not only complicates a solid electrolyte system, a preparation process and operation, but also greatly reduces the performance because the component is in a liquid state (the thermal stability can only reach 180 ℃) under the high-temperature condition, so that the safety problems of electrolyte leakage and the like of the battery can not be avoided. (Journal of Applied Polymer Science 2018,135.9:45838.) the electrolyte systems studied by Grewal (Polymer International 2019,68.4: 684-containing 693.) and Lim (Journal of Membrane Science 2019, (589)). The component has the function of partially transferring ions when the former system is used as a part of a framework, but needs later-stage swelling electrolyte to greatly improve the electrochemical performance; the latter system is cross-linked with BAGDE to be used as a structural material, but the ion transmission function is required to depend on EMIMTFSI ionic liquid. The two types of elastic full-solid electrolytes do not belong to the elastic full-solid electrolyte with a cross-linking structure in the true sense, the preparation cost is greatly improved due to the increase of the number of system and process operations or the technical difficulty, and the popularization benefit is limited.
Chinese patent application publication No. CN101440177A discloses a polymer solid electrolyte prepared by blending epoxy resin and nitrile rubber, which uses epoxy resin as an additive to improve toughness and heat resistance by using a bisphenol a skeleton.
Chinese patent publication No. CN105355974A discloses a solid electrolyte obtained by lithium ion treatment of a cross-linked polysulfone/polyethylene oxide composite with an ion exchange liquid, in which epoxy resin is used, but only the reactivity of epoxy group is used for cross-linking, and the main material is not epoxy resin, and epoxy resin is not really used for the electrolyte.
Chinese patent application with publication number CN108365262A discloses an organic fertilizerInorganic composite electrolytes, although epoxy resins are incorporated into the system, their main purpose is to utilize the crosslinked network of epoxy resins as a backbone support. Therefore, the system still adds more than 50 percent of linear polymer and inorganic oxide electrolyte nano particles in the system to provide the function of ionic conduction, but the ionic conductivity at room temperature is only barely 10-5And S/cm grade. In addition, the types of epoxy resins utilized are limited, limited to glycidyl ether type epoxy resins, which greatly limits the application range of the epoxy resin system. And the preparation method of the solid electrolyte using the solvent is complex and the process is complicated.
The preparation processes described in these documents and patents above all use organic solvents. The method is harmful to human health and ecological environment, and also introduces impurities, increases the difficulty of preparation operation, and increases the process cost. There is therefore a need to introduce a simple process for the preparation of solvent-free, extremely simple systems of virtually all solid-state elastomer electrolytes.
In addition, since most manufacturing methods choose to use a solvent, the battery assembly must be performed after the solvent is completely volatilized. There are three disadvantages to this method of preparing an electrolyte, and first, when the electrolyte prepared in this way is in contact with an electrode, there are gaps at the solid-solid contact interface, which may result in an increase in the interfacial resistance of the battery and a decrease in the cycle performance. Secondly, the evaporation of the solvent may cause pores in the electrolyte, which is detrimental to cation transport. Finally, since the solvent exists inside the electrolyte, there is a high possibility that the solvent remains. The solvent-free method for preparing the electrolyte can adopt an in-situ curing mode, thereby perfectly solving the problem.
Disclosure of Invention
Aiming at the technical problems of introduction of impurities and solvent in the preparation process of the existing cross-linked solid polymer electrolyte and narrow working temperature range of the existing thermoplastic polymer solid electrolyte, the invention introduces an epoxy resin system, provides an elastomer epoxy resin-based all-solid electrolyte membrane with high temperature resistance, high flexibility and simple preparation process and a preparation method without solvent, reduces the harm to human bodies and environment and reduces the possibility of pores in the electrolyte.
The invention provides an elastomer epoxy resin-based all-solid-state electrolyte which is prepared from a precursor solution, and is characterized in that the precursor solution only consists of an epoxy resin monomer, a curing agent and an alkali metal salt; the alkali metal salt is dissociated into alkali metal cations by solvation of the epoxy resin monomer with the curing agent; the epoxy resin monomer and the curing agent are subjected to a crosslinking reaction, and the obtained electrolyte is an elastomer electrolyte self-supporting membrane which is used as a framework of the electrolyte and is responsible for ion transmission.
Preferably, the epoxy resin monomer is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxy alkene epoxy resin and derivatives thereof.
Preferably, the epoxy resin monomer is a bio-based epoxy resin, especially one or more of polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and itaconic acid based epoxy resin.
Preferably, the curing agent is a polyether amine curing agent.
Preferably, the alkali metal salt is one or more of lithium salt or sodium salt; the lithium salt is LiPF6、LiClO4、LiTFSI、LiFSI、LiTf、LiBF4LiBOB, LiDFOB, LiTDI; the sodium salt is NaPF6、NaClO4、NaTFSI、NaFSI、NaTf、NaBF4、NaBOB、NaDFOB、NaTDI。
The invention also provides a preparation method of the elastomer epoxy resin-based all-solid-state electrolyte, which is characterized by comprising the following steps of: (1) respectively adding the dried alkali metal salt into an epoxy resin monomer and a curing agent, and stirring in a glove box filled with argon until the alkali metal salt is completely dissolved; (2) adding the epoxy resin monomer dissolved with the alkali metal salt and the curing agent into a container, uniformly stirring, then putting into a glove box transition cabin, vacuumizing, and carrying out ultrasonic treatment; (3) spreading release paper between the two glass plates, adding the mixed liquid obtained in the step (2) after ultrasonic treatment, and clamping a cover glass at the edge to control the thickness; and fully curing in a vacuum oven to obtain the electrolyte film in an elastomer state.
Preferably, the alkali metal salt in said step (1) is mixed with the epoxy resin monomer and the curing agent according to Li+: o is 1 (20 to 100), and the mixture is sufficiently stirred to completely dissolve the alkali metal salt.
Preferably, the molar number of the epoxy resin monomer and the curing agent in the step (2) is: molar number of active groups of curing agent is 1: (0.4-1.1), and fully stirring to mix the two phases.
The invention also provides application of the elastomer epoxy resin-based all-solid-state electrolyte in a double-steel battery.
Preferably, the application of the elastomer epoxy resin-based all-solid-state electrolyte in the double-steel battery provided by the invention comprises the following steps: (a) respectively adding the dried alkali metal salt into an epoxy resin monomer and a curing agent, and stirring in a glove box filled with argon until the alkali metal salt is completely dissolved; (b) adding the epoxy resin monomer dissolved with the alkali metal salt and the curing agent into a container, uniformly stirring, then putting into a glove box transition cabin, vacuumizing, and carrying out ultrasonic treatment; (c) dripping the ultrasonically treated mixed liquid obtained in the step (b) on a steel sheet (the steel sheet is used as a blocking electrode), covering another steel sheet after short-time heating, continuously heating on a heat table of a glove box, and assembling a double-steel battery; (d) placing the elastomer epoxy resin-based all-solid-state electrolyte dual-steel battery assembled in the step (c) into a vacuum oven for continuous curing; the alkali metal salt in the step (a) is mixed with the epoxy resin monomer and the curing agent according to Li+: preparing O1 (20-100) in a molar ratio, and fully stirring to completely dissolve the alkali metal salt; the epoxy resin monomer and the curing agent in the step (b) are mixed according to the epoxy group molar number: molar number of active groups of curing agent is 1: (0.4-1.1), and fully stirring to mix the two phases.
The invention has the following beneficial effects:
(1) in the invention, the precursor solution is only composed of the ternary system of the epoxy resin monomer, the curing agent and the alkali metal salt, and the system is pure and is beneficial to greatly improving the performance of the battery.
(2) The elastomer epoxy resin-based all-solid-state electrolyte system provided by the invention can be used as a matrix by matching different epoxy resins and curing agents, which is one of the reasons for selecting the epoxy resin system. By comparing various epoxy resin systems, relating to preparation processes and performance tests, the whole epoxy resin system is applied to an electrolyte matrix, and the design of a formula and the selection of the process become very flexible. The epoxy resin as thermosetting resin forms a stable cross-linking structure with the curing agent after being cured at high temperature, and can improve the mechanical property of the solid electrolyte. The electrolyte matrix has good compatibility with alkali metal, is suitable for batteries of lithium metal and the like, and greatly improves the energy density of the batteries.
(3) The epoxy resin-based solid electrolyte provided by the invention has the best cross-linking network density, shows a high elastic state and certain toughness macroscopically, has better flexibility, has basic conditions of an electrolyte matrix capable of transmitting ions, and is beneficial to improving the ionic conductivity. Compared with PEO-based electrolyte, the epoxy resin-based all-solid electrolyte provided by the invention does not crystallize at room temperature, does not melt at high temperature, and has a wide application temperature range.
(4) The preparation process provided by the invention is simple, does not need an initiator or a solvent in the production and processing process, is environment-friendly, has low cost, and is easy to realize industrial production and commercial application. And because the reaction does not need a solvent, the epoxy resin-based all-solid-state electrolyte can be used for preparing an all-battery in an in-situ curing mode, and the interface contact between the electrolyte and an electrode is greatly optimized. The electrolyte system without liquid greatly reduces the occurrence of potential safety hazard and conforms to the future development planning of the battery industry.
Drawings
Fig. 1 is an all-solid-state electrolyte of the present invention.
FIG. 2 is a DSC of an all-solid-state electrolyte according to the present invention.
FIG. 3a is a sectional electron micrograph of an electrolyte/electrode according to the present invention; FIG. 3b is a mapping diagram of the P element of the present invention; FIG. 3c is a mapping diagram of the N element of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Polyethylene glycol diglycidyl ether (PEGDGE), polyetheramine (D2000) and lithium bistrifluoromethanesulfonimide (LiTFSI) were previously dried in a vacuum oven.
(2) The PEGDGE and the LiTFSI (mass ratio of 1:0.22) are added into a screw bottle in a glove box, and the mixture is stirred for 12 hours (the rotating speed is 200r/min) at the constant temperature of 50 ℃ until the lithium salt is completely dissolved. Similarly, D2000 and LiTFSI (mass ratio of 1: 0.25) are added into a screw bottle and stirred for 12 hours (rotation speed of 200r/min) at a constant temperature of 50 ℃ until the lithium salt is completely dissolved.
(3) And (3) adding the PEGDGE and the D2000 (in a mass ratio of 2:3) in which the LiTFSI is dissolved in the step (2) into a screw bottle, and stirring for 0.5h (at a rotation speed of 200r/min) at a constant temperature of 50 ℃ until the system is uniformly mixed.
(4) And (4) putting the mixed liquid obtained in the step (3) into a glove box transition cabin, vacuumizing, and carrying out ultrasonic treatment for 0.5h to remove bubbles in the mixed liquid.
(5) Spreading release paper on the two glass plates, adding the mixed liquid obtained in the step (4) after ultrasonic treatment, and clamping a cover glass at the edge to control the thickness. Curing at 100 deg.C under vacuum for more than 3h ensures sufficient curing. And taking out the mold from the vacuum oven, and removing the glass plate and the release paper to obtain the all-solid-state electrolyte material with the cross-linked structure.
(6) Cutting the all-solid-state electrolyte material in the step (5) into a disc shape with the diameter of 16mm, and assembling the disc-shaped electrolyte material into a battery in a glove box filled with argon.
(7) The conductivity of the epoxy resin-based all-solid-state electrolyte is tested to be 4.31 multiplied by 10 under the condition of 25 ℃ by using an alternating current impedance method-6S/cm。
Example 2
(1) Polyethylene glycol diglycidyl ether (PEGDGE), polyetheramine (D900) and lithium bistrifluoromethanesulfonimide (LiTFSI) were previously dried in a vacuum oven.
(2) Putting PEGDGE and D900(1:1.4) into a screw bottle, adding a proper amount of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) (the mass ratio of PEGDGE + D900 to LiTFSI is 1:0.1), and stirring for 12 hours (the rotating speed is 200r/min) at the constant temperature of 50 ℃ until the lithium salt is completely dissolved.
(3) Quickly transferring the mixed liquid into a vacuum-pumping device, and pumping the gas in the mixed liquid in the screw bottle as clean as possible.
(4) And quickly pouring the mixed liquid after vacuum treatment into the lower half mold, putting the lower half mold into a vacuum oven, quickly placing the upper half mold, and continuously curing for 3 hours at the vacuum condition of 100 ℃.
And taking out the mold from the vacuum oven, and removing the glass plate and the release paper to obtain the all-solid-state electrolyte material with the cross-linked structure.
(5) Cutting the all-solid-state electrolyte material in the last step into a disc shape with the diameter of 16mm, and assembling the disc-shaped all-solid-state electrolyte material into a battery in a glove box filled with argon.
(6) The conductivity of the solid electrolyte of the cross-linked structure was measured under different temperature conditions using the ac impedance method as shown in the following table:
example 3
(1) Polyethylene glycol diglycidyl ether (PEGDGE), polyetheramine (D900) and lithium bistrifluoromethanesulfonimide (LiTFSI) were previously dried in a vacuum oven.
(2) Putting PEGDGE500 and D900(1:1.4) into a screw bottle, adding a proper amount of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) (the mass ratio of PEGDGE + D900 to LiTFSI is 1:0.4), and stirring for 12 hours (the rotating speed is 200r/min) at the constant temperature of 50 ℃ until the lithium salt is completely dissolved.
(3) Quickly transferring the mixed liquid into a vacuum-pumping device, and pumping the gas in the mixed liquid in the screw bottle as clean as possible.
(4) And quickly pouring the mixed liquid after vacuum treatment into the lower half mold, putting the lower half mold into a vacuum oven, quickly placing the upper half mold, and continuously curing for 3 hours at the vacuum condition of 100 ℃.
And taking out the mold from the vacuum oven, and removing the glass plate and the release paper to obtain the all-solid-state electrolyte material with the cross-linked structure.
(5) Cutting the all-solid-state electrolyte material in the last step into a disc shape with the diameter of 16mm, and assembling the disc-shaped all-solid-state electrolyte material into a battery in a glove box filled with argon.
(6) The conductivity of the solid electrolyte of the cross-linked structure was measured under different temperature conditions using the ac impedance method as shown in the following table:
example 4
(1) Polyethylene glycol diglycidyl ether (PEGDGE), polyetheramine (D230) and lithium bistrifluoromethanesulfonimide (LiTFSI) were previously dried in a vacuum oven.
(2) Putting PEGDGE and D230(1:0.4) into a screw bottle, adding a proper amount of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) (the mass ratio of PEGDGE + D230 to LiTFSI is 1:0.1), and stirring for 12 hours (the rotating speed is 200r/min) at the constant temperature of 50 ℃ until the lithium salt is completely dissolved.
(3) Quickly transferring the mixed liquid into a vacuum-pumping device, and pumping the gas in the mixed liquid in the screw bottle as clean as possible.
(4) And quickly pouring the mixed liquid after vacuum treatment into the lower half mold, putting the lower half mold into a vacuum oven, quickly placing the upper half mold, and continuously curing for 3 hours at the vacuum condition of 100 ℃.
And taking out the mold from the vacuum oven, and removing the glass plate and the release paper to obtain the all-solid-state electrolyte material with the cross-linked structure.
(5) Cutting the all-solid-state electrolyte material in the last step into a disc shape with the diameter of 16mm, and assembling the disc-shaped all-solid-state electrolyte material into a battery in a glove box filled with argon.
(6) The conductivity of the solid electrolyte of the cross-linked structure was measured under different temperature conditions using the ac impedance method as shown in the following table:
example 5
(1) Polyethylene glycol diglycidyl ether (PEGDGE), polyetheramine (D900) and lithium bistrifluoromethanesulfonimide (LiTFSI) were previously dried in a vacuum oven.
(2) The PEGDGE and the LiTFSI (mass ratio of 1:0.4) are added into a screw bottle in a glove box, and the mixture is stirred for 12 hours (the rotating speed is 200r/min) at the constant temperature of 50 ℃ until the lithium salt is completely dissolved. Similarly, D900 and LiTFSI (mass ratio of 1:0.4) are added into a screw-top bottle and stirred for 12 hours (rotation speed of 200r/min) at a constant temperature of 50 ℃ until the lithium salt is completely dissolved.
(3) Adding PEGDGE and D900 (mass ratio of 2:3) dissolved with LiTFSI into a screw bottle, and stirring at 50 deg.C for 30min (rotation speed of 200r/min) until the system is mixed uniformly.
(4) And putting the mixed liquid after vacuum treatment into a glove box transition cabin for vacuumizing, and carrying out ultrasonic treatment for 0.5h to remove bubbles in the mixed liquid.
(5) Dripping the ultrasonically treated mixed liquid on a steel sheet (the steel sheet is used as a blocking electrode), heating for 10min, covering another steel sheet, continuously heating on a glove box hot table, and assembling a double-steel battery;
(6) and placing the assembled elastomer epoxy resin-based all-solid-state electrolyte dual-steel battery into a vacuum oven to continuously cure for 2-5 hours.
(7) The conductivity of the solid electrolyte of the cross-linked structure was measured under different temperature conditions using the ac impedance method as shown in the following table:
as shown in fig. 3a, 3b, and 3c, the lithium iron phosphate positive electrode of the present invention is made of LiFePO4The super P and the PVDF are mixed according to the mass ratio of 8: 1:1 is prepared. P, F, Fe is derived from PVDF and LiFePO in the electrode4The main distribution and electrode layers are seen from the figure; s, N from LiTFSI and D2000 in the electrolyte, evenly distributed in the electrolyte and electrode layers, illustrateThe electrolyte can well permeate into the holes of the electrode, thereby greatly improving the electrochemical performance.
Fig. 3a is a sectional electron microscope image of the electrolyte/electrode, which can clearly see the electrolyte layer and the electrode layer, wherein the electrode layer is in a porous state, and if the in-situ solidification method of the invention is not used, the solid electrolyte is difficult to permeate into the pores of the electrode, which can cause poor contact between the electrolyte and the electrode, and greatly reduce the utilization rate of the active material. In the in-situ solidification method, the electrolyte can fully permeate into the holes of the electrode, and the electrolyte is fully contacted with the electrode.
Fig. 3b is a mapping graph of P element, which shows the distribution of P element, wherein the P element is from the electrode active material LiFePO4, and it can be seen from the graph that the P element is mainly distributed in the electrode layer, representing the distribution of the electrode active material.
Fig. 3c is a mapping graph of N elements, which shows the distribution of N elements, wherein the N elements mainly come from an electrolyte matrix and lithium salt (LiTFSI), and it can be seen from the graph that the N elements are uniformly distributed in an electrolyte and an electrode layer, which indicates that the electrolyte can well penetrate into pores of an electrode during the in-situ preparation of a battery, and thus, a good electrode/electrolyte interface contact is achieved.
Comparative example
By taking the Chinese invention patent application with the publication number of CN108365262A as a comparative example, the invention has the following advantages:
firstly, the system of the invention is a simple ternary system of epoxy resin monomer, curing agent and lithium salt, while the system of the patent application No. CN108365262A contains glycidyl ether epoxy resin, cross-linking agent, linear polymer and inorganic particles. Wherein, the types of the components in the system are also different: the resin in the patent application system of CN108365262A only uses glycidyl ether epoxy resin, and focuses on ether bonds in the epoxy resin and benzene rings for constructing a skeleton; the epoxy resin monomer used in the patent is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxy alkene epoxy resin and derivatives thereof, and the molecules contain polar groups such as ether bonds, ester groups and the like which are mainly used for dissolving lithium salts.
Secondly, the two ion conduction pathways differ. The patent application No. CN108365262A utilizes linear polymer and inorganic particles added in the system to conduct lithium ions, the cross-linked network-shaped electrolyte obtained by the system is an elastomer electrolyte, molecular chains have good flexibility, the epoxy resin networks can be used for conducting ions (including lithium ions, sodium ions and the like), and the conductivity can reach 10 at room temperature-5S/cm。
Finally, the application of the patent No. CN108365262A still uses a solvent during preparation, but the invention provides a solvent-free preparation method, which has extremely simple preparation process and safe and environment-friendly production and use.
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.
Claims (10)
1. An elastomer epoxy resin-based all-solid-state electrolyte is prepared from a precursor solution, and is characterized in that the precursor solution only consists of an epoxy resin monomer, a curing agent and an alkali metal salt;
the alkali metal salt is dissociated into alkali metal cations by solvation of the epoxy resin monomer with the curing agent;
the epoxy resin monomer and the curing agent are subjected to a crosslinking reaction, and the obtained electrolyte is an elastomer electrolyte self-supporting membrane which is used as a framework of the electrolyte and is responsible for ion transmission.
2. The elastomer epoxy resin-based all-solid-state electrolyte according to claim 1, wherein the epoxy resin monomer is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxy alkene epoxy resin, and derivatives thereof.
3. The elastomer epoxy resin-based all-solid-state electrolyte according to claim 1 or 2, wherein the epoxy resin monomer is a bio-based epoxy resin, and the bio-based epoxy resin is one or more of polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and itaconic acid-based epoxy resin.
4. The elastomer epoxy resin-based all-solid-state electrolyte as claimed in claim 1, wherein said curing agent is a polyetheramine-based curing agent.
5. The elastomeric epoxy resin based all solid state electrolyte according to claim 1, characterized in that said alkali metal salt is one or more of a lithium salt or a sodium salt;
the lithium salt is LiPF6、LiClO4、LiTFSI、LiFSI、LiTf、LiBF4、LiBOB、LiDFOB、LiTDI；
The sodium salt is NaPF6、NaClO4、NaTFSI、NaFSI、NaTf、NaBF4、NaBOB、NaDFOB、NaTDI。
6. The method for preparing an elastomer epoxy resin-based all-solid-state electrolyte according to claim 1, comprising the steps of:
(1) respectively adding the dried alkali metal salt into an epoxy resin monomer and a curing agent, and stirring in a glove box filled with argon until the alkali metal salt is completely dissolved;
(2) adding the epoxy resin monomer dissolved with the alkali metal salt and the curing agent into a container, uniformly stirring, then putting into a glove box transition cabin, vacuumizing, and carrying out ultrasonic treatment;
(3) spreading release paper between the two glass plates, adding the mixed liquid obtained in the step (2) after ultrasonic treatment, and clamping a cover glass at the edge to control the thickness; and fully curing in a vacuum oven to obtain the electrolyte film in an elastomer state.
7. The method of claim 6, wherein the epoxy resin-based all-solid-state electrolyte is an elastomerIn the step (1), the alkali metal salt, the epoxy resin monomer and the curing agent are Li+: o is 1 (20 to 100), and the mixture is sufficiently stirred to completely dissolve the alkali metal salt.
8. The method for preparing elastomer epoxy resin-based all-solid-state electrolyte according to claim 6, wherein the molar ratio of epoxy resin monomer to curing agent in step (2) is as follows: molar number of active groups of curing agent is 1: (0.4-1.1), and fully stirring to mix the two phases.
9. Use of the elastomeric epoxy resin based all solid state electrolyte of claim 1 in a bi-steel battery.
10. Use of an elastomeric epoxy resin based all solid state electrolyte in a bi-steel battery according to claim 9, characterized in that it comprises the steps of:
(a) respectively adding the dried alkali metal salt into an epoxy resin monomer and a curing agent, and stirring in a glove box filled with argon until the alkali metal salt is completely dissolved;
(b) adding the epoxy resin monomer dissolved with the alkali metal salt and the curing agent into a container, uniformly stirring, then putting into a glove box transition cabin, vacuumizing, and carrying out ultrasonic treatment;
(c) dripping the ultrasonically treated mixed liquid obtained in the step (b) on a steel sheet serving as a blocking electrode, covering another steel sheet after short-time heating, continuously heating on a glove box hot table, and assembling a double-steel battery;
(d) placing the elastomer epoxy resin-based all-solid-state electrolyte dual-steel battery assembled in the step (c) into a vacuum oven for continuous curing;
the alkali metal salt in the step (a) is mixed with the epoxy resin monomer and the curing agent according to Li+: preparing O1 (20-100) in a molar ratio, and fully stirring to completely dissolve the alkali metal salt;
the epoxy resin monomer and the curing agent in the step (b) are mixed according to the epoxy group molar number: molar number of active groups of curing agent is 1: (0.4-1.1), and fully stirring to mix the two phases.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113140789A (en) * | 2021-04-22 | 2021-07-20 | 北京化工大学 | Recyclable self-repairing gel-state electrolyte and preparation method and application thereof |
| CN114050314A (en) * | 2021-11-12 | 2022-02-15 | 华东理工大学 | Epoxy resin-based ionic gel electrolyte and preparation method thereof |
| CN115911562A (en) * | 2022-12-30 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246964A (en) * | 2008-01-31 | 2008-08-20 | 上海交通大学 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
| CN107129663A (en) * | 2017-06-12 | 2017-09-05 | 陈伟 | Mems structure dielectric of good mechanical properties and preparation method thereof |
-
2020
- 2020-11-17 CN CN202011284988.0A patent/CN112421104A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246964A (en) * | 2008-01-31 | 2008-08-20 | 上海交通大学 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
| CN107129663A (en) * | 2017-06-12 | 2017-09-05 | 陈伟 | Mems structure dielectric of good mechanical properties and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KOZO MATSUMOTO: "Confinement of Ionic Liquid by Networked Polymers Based on Multifunctional Epoxy Resins", 《MACROMOLECULES》 * |
| THI KHANH LY NGUYEN: "1,2,3-Triazolium-Based Epoxy–Amine Networks: Ion-Conducting Polymer Electrolytes", 《MACROMOLECULAR RAPID COMMUNICATIONS 》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113140789A (en) * | 2021-04-22 | 2021-07-20 | 北京化工大学 | Recyclable self-repairing gel-state electrolyte and preparation method and application thereof |
| CN114050314A (en) * | 2021-11-12 | 2022-02-15 | 华东理工大学 | Epoxy resin-based ionic gel electrolyte and preparation method thereof |
| CN115911562A (en) * | 2022-12-30 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
| CN115911562B (en) * | 2022-12-30 | 2023-11-28 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
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