CN111261937A - PEO polymer-based 3D network structure all-solid-state electrolyte for all-solid-state lithium ion battery and preparation method thereof - Google Patents
PEO polymer-based 3D network structure all-solid-state electrolyte for all-solid-state lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solid electrolytes, and particularly relates to a PEO polymer-based 3D network structure all-solid electrolyte for an all-solid lithium ion battery and a preparation method thereof. The 3D network structure all-solid-state electrolyte is prepared by selecting modified graphene aerogel as a network framework, selecting polyethylene oxide (PEO) as a high polymer matrix, selecting a blending reactant of polyethylene glycol (PEG), fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) as a plasticizer, blending PEO, lithium bistrifluoromethylsulfonyl imide (LiTFSI) and the plasticizer, and pouring a blending solution into the modified graphene aerogel. Compared with the traditional PEO all-solid-state electrolyte, the 3D network structure all-solid-state electrolyte prepared by the invention has better charge and discharge performance and cycle performance.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to a PEO polymer-based 3D network structure all-solid electrolyte for an all-solid lithium ion battery and a preparation method thereof.
Background
Solid electrolytes (SPE) have significant processing advantages over liquids, but generally have poor mechanical properties and are difficult to effectively suppress the formation of lithium dendrites. Moreover, the lithium ion conductivity of the SPE is lower than that of the liquid state by at least 2-3 orders of magnitude, so that the capacity of fast charging of the solid-state battery at the ambient temperature is limited. It is common to reinforce lithium in several ways, one of which is the addition of inorganic fillers to the SPE to enhance ionic conductivity. However, inorganic fillers tend to agglomerate, reducing their effectiveness in interacting with lewis acids and bases, and the increased ionic conductivity is insufficient to achieve qualitative changes. Furthermore, the filler cannot form an interconnected reinforcing structure to effectively improve the mechanical properties of the solid electrolyte. The electrolyte prepared by the method has insufficient ionic conductivity and mechanical property to meet the commercial requirement. Another approach is to incorporate a plasticizer into the lithium salt/polymer blend to significantly increase the ionic conductivity to a practical value, but at the expense of further reduction in mechanical properties and increased flammability. A third new approach is to blend polymer electrolytes with inorganic ions for conductors, and while further improvements in ionic conductivity have been successfully demonstrated, mechanical properties and thermal stability remain to be improved. In fact, the ionic conductivity is often contradictory to the elastic modulus in SPEs, and high ionic conductivity generally requires lower crystallinity and more mobile polymer chains, which in turn leads to polymers with poorer mechanical properties.
Disclosure of Invention
Aiming at the problems of lithium dendrites in the SPE charging and discharging process and low conductivity at room temperature in the prior art, the improved graphene aerogel is used for carrying out structural reinforcement on the PEO-based electrolyte. In this design, the unique properties of the aerogel can play a key role: by incorporating the modified graphene aerogel backbone, the mechanical properties of the composite electrolyte are significantly improved, thereby enabling the electrolyte to mechanically inhibit the growth of Li dendrites; the high porosity further facilitates a large occupancy of the polymer electrolyte in the composite, thereby enabling more efficient lithium ion conduction.
The invention provides a PEO polymer-based 3D network structure all-solid-state electrolyte, which is prepared by selecting modified graphene aerogel as a network framework, selecting polyethylene oxide (PEO) as a high polymer matrix, selecting a blending reactant of polyethylene glycol (PEG), fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) as a plasticizer, blending PEO, lithium bistrifluoromethylsulfonyl imide (LiTFSI) and the plasticizer, and pouring a blending solution into the modified graphene aerogel.
The invention also provides a preparation method of the PEO polymer-based 3D network structure all-solid-state electrolyte, which comprises the following specific steps:
(1) pre-strengthening graphene by using Polyimide (PI) to obtain a graphene oxide mixed solution;
dispersing 0.1-0.4 g of 4, 4 '-diaminodiphenyl ether (ODA) into 20-50 mL of Dimethylacetamide (DMAC), adding 0.3-0.7 g of 4, 4' -diphenyl ether dianhydride (ODPA) under stirring, stirring for 1h, centrifuging at 5000r/min, dropwise adding the obtained bottom layer filtrate into ionized water to generate PAA precipitate, carrying out cold drying on the precipitate to obtain PAA powder, dissolving 0.03-0.08 PAA in 1mL of deionized water and 0.01g of Triethylamine (TEA) mixed solvent to obtain PAA solution, and uniformly mixing 1mL of PAA solution and 20-30 mL of graphene oxide solution to obtain the graphene oxide mixed solution.
(2) Performing secondary reinforcement modification on the graphene aerogel by Polydimethylsiloxane (PDMS);
taking a positive shell of a CR2032 button cell as a reaction vessel, moving 300 mu L of the graphene oxide mixed solution obtained in the step (1), putting the positive shell containing the graphene mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 24h to obtain a graphene hydrogel sheet, freezing the hydrogel sheet at-80 ℃ for 10h, then vacuumizing to-0.1 MPa, freeze-drying for 24h, directly soaking the obtained aerogel into a PDMS solution after cold drying, wherein the PDMS solution comprises the following components: curing agent (ethyl orthosilicate): n-hexane 10: 1: weighing 1000 parts by weight, soaking for 6 hours, taking out, heating in a glove box to 60 ℃, and drying to obtain the modified graphene aerogel skeleton.
(3) Preparing a blend of PEG, FEC and VC according to the weight ratio, and heating to react to obtain a plasticizer;
all reagents used need to be dried in vacuum at 80 ℃ for 24h, and the components are as follows: FEC: VC is 2: 1: 1, wherein the PEG is taken in an amount range of 0.3-0.7 g, acetonitrile is selected as an auxiliary solvent, the mixture is stirred and reacted in a glove box at 60 ℃ for 2 hours, the rotating speed is 1250r/min, and the temperature of the solution is always controlled to be about 40 ℃ after the reaction is finished.
(4) Weighing PEO and LiTFSI reagents according to the EO/Li ratio and dissolving the PEO and the LiTFSI reagents in an acetonitrile reagent to obtain a precursor solution;
the used PEO (average Mv-300,000) and LiTFSI reagents need to be dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding LiTFSI and PEO reagents into the acetonitrile under stirring, wherein the rotation speed is 1400r/min, and reacting at room temperature for 24 hours, wherein the experimental processes are all carried out in a glove box.
(5) Adding a plasticizer into the precursor solution and blending to obtain a blended solution;
in the solution mixing process, the precursor solutions obtained in the steps (3) and (4) are controlled to operate at 40 ℃, the addition amount of the plasticizer accounts for 10-20% of the total mass of the PEO and the lithium salt, the plasticizer in the step (3) is dropwise added into the PEO precursor electrolyte in the step (4) under stirring, the rotating speed is 600r/min, after the dropwise addition is finished, the temperature is kept at 40 ℃ for 30min, and then the mixture is naturally cooled to room temperature and stirred for 2h, so that a blending solution is obtained.
(6) Pouring the blend into the modified graphene aerogel to obtain the novel all-solid-state electrolyte.
And (3) pouring on a polytetrafluoroethylene plate, dripping 5-10 ml of the blending liquid obtained in the step (5) by using a dropper to the surface of the graphene aerogel sheet obtained in the step (2), naturally infiltrating for 2h, wiping off redundant electrolyte on the surface by absorbent cotton, naturally drying for 5h, turning to the back, and repeating the pouring step to obtain the 3D network structure all-solid-state electrolyte.
(7) Selecting lithium iron phosphate (LiFePO)4) Taking polyvinylidene fluoride (PVDF) and the precursor solution obtained in the step (4) as an adhesive, and taking super P and acetylene black as conductive agents to prepare a positive plate required by the test;
the distribution ratio of the pole piece group is LiFePO4: (superP: acetylene black): (PVDF: electrolyte precursor) 7: (0.5:0.5): (1: 1), manually grinding the anode precursor until a mirror effect is achieved, smearing a smear on an aluminum foil by using a scraper with scales of 150 microns, standing for 2 hours in vacuum, heating to 60 ℃, drying for 12 hours, taking out, and cutting into pieces to obtain the anode piece.
(8) Selecting a lithium plate as a negative electrode, assembling a CR2025 button cell, putting the cell components into a positive electrode shell according to the sequence of a lithium iron phosphate positive electrode/electrolyte/lithium negative electrode, covering the negative electrode shell, moving to a button press, pressurizing to 50kg of pressure, maintaining the pressure for 4-5 seconds to obtain the button cell, and carrying out heat preservation and pressure maintenance treatment before a charge-discharge test.
The assembled battery needs to be kept at 50 ℃ for 24h, and then taken out to be kept at 10MPa for 5 min. The charge and discharge test temperature was 50 ℃.
Has the advantages that:
(1) in the solution obtained in the step (5), the affinity of the plasticizer molecular chain to a PEO long chain with large molecular weight is enhanced, so that PEO is promoted to dissociate more free chain segments, and the ionic conductivity of the obtained integral electrolyte is increased.
(2) According to the method, graphene oxide is independently modified, then is subjected to hydrothermal cold drying treatment to prepare graphene aerogel, and then is compounded with the polymer electrolyte to obtain the solid electrolyte, so that short circuit in the battery caused by the conductive property of the graphene can be avoided to a great extent; compared with the common polymer dielectric medium, the solid electrolyte provided by the invention can effectively promote the coordination and unification of the battery cycle stability and the mechanical and thermal stability performance of the electrolyte, and can effectively prolong the service life of the battery and improve the charge-discharge specific capacity.
Drawings
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams only illustrating the basic morphology and properties of the electrolyte according to the invention in a schematic way, and therefore they show only the constituents relevant to the invention.
FIG. 1 is a macroscopic sample view of a 3D network structured electrolyte;
FIG. 2 is a charge-discharge curve of the battery obtained in example 1 at different rates at 50 ℃;
FIG. 3 is a graph showing rate capability at 50 ℃ of the battery obtained in example 1.
The curve ① shown in FIG. 4 corresponds to the battery charging and discharging performance of the electrolyte of comparative examples 1, 2 and 3, and ④ is the charging and discharging curve of the electrolyte battery with a 3D network structure modified in example 1 of the invention.
FIG. 5 is a battery charge and discharge curve of the electrolyte described in comparative example 4;
fig. 6 is a battery charge and discharge curve of the electrolyte described in comparative example 5.
Detailed Description
Note that the graphene oxide solution used in the present invention was prepared by a conventional Hummers method.
Example 1
(1) Preparing a PAA | graphene oxide mixed solution: dispersing 0.325g of 4, 4 '-diaminodiphenyl ether (ODA) into 30mL of Dimethylacetamide (DMAC), adding 0.583g of 4, 4' -diphenyl ether dianhydride (ODPA) while stirring, stirring for 1h, centrifuging at 5000r/min, dropwise adding the obtained bottom layer filtrate into ionized water to generate PAA precipitate, and carrying out cold drying on the precipitate to obtain PAA powder. 0.054g of PAA body is dissolved in 1mL of deionized water and 0.01g of Triethylamine (TEA) mixed solution, and the 1mL of mixed solution and 20mL of graphene oxide solution are mixed uniformly.
(2) Based on the consideration of the diameter and the thickness of an electrolyte film, a CR2032 positive shell is selected as a hydrothermal reaction vessel, and the specific operation is as follows: transferring 300 mu L of graphene oxide mixed solution, carrying out hydrothermal reaction at 120 ℃ for 24h to obtain a graphene hydrogel sheet, freezing the hydrogel sheet at-80 ℃ for 10h, vacuumizing to-0.1 MPa at the temperature, drying for 24h, directly soaking the obtained aerogel into the mixed solution of PDMS, wherein the solution comprises the following components in percentage by weight: curing agent: n-hexane 10: 1: weighing 1000 parts by weight, soaking for 6 hours, taking out, heating in a glove box to 60 ℃, and drying to obtain the modified graphene aerogel skeleton.
(3) All reagents used for blending the plasticizer are required to be dried in vacuum at 80 ℃ for 24h, and the components are as follows: FEC: VC is 2: 1: weighing 0.5g, 0.25g and 0.25g of 1 by weight, selecting 2g of acetonitrile as an auxiliary solvent to accelerate dissolution, stirring and reacting in a glove box at 60 ℃ for 2 hours at the rotating speed of 1250r/min, and controlling the temperature of the solution to be about 40 ℃ all the time after the reaction is finished.
(4) PEO (average Mv-300,000) and a LiTFSI reagent used in the electrolyte are dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding LiTFSI and PEO reagents into the acetonitrile under stirring, wherein the rotation speed is 1400r/min, and reacting at room temperature for 24 hours, wherein the experimental processes are all carried out in a glove box.
(5) And (3) heating all the PEO-based electrolyte precursor obtained in the step (4) to 40 ℃, slowly dripping 0.25g of the blending plasticizer under the stirring condition, rotating at the speed of 600r/min, keeping the temperature at 40 ℃ for 30min after finishing dripping, and naturally cooling to room temperature and stirring for 2 h.
(6) And (3) dropping excessive electrolyte obtained in the step (5) on a polytetrafluoroethylene plate by using a dropper to the surface of the graphene aerogel sheet obtained in the step (2), naturally soaking for 2h, wiping off the excessive electrolyte on the surface by using absorbent cotton, naturally drying for 5h, turning to the back, and repeating the pouring step to obtain the 3D network structure all-solid-state electrolyte. Fig. 1 is a diagram showing a sample of a novel 3D network structure all-solid-state electrolyte according to the present invention.
(7) The distribution ratio of the positive electrode plate group is LiFeSO4: (superP: acetylene black): (PVDF: electrolyte precursor) 7: (0.5:0.5): (1: 1), respectively weighing 0.7g, (0.05g ), 0.1g and 0.1g of the positive electrode, transferring the mixture into a grinding pot, uniformly mixing, manually grinding until the positive electrode precursor presents a mirror surface effect, smearing the positive electrode precursor on an aluminum foil by using a scraper with a scale of 150 microns, standing the mixture in vacuum for 2 hours, heating the mixture to 60 ℃, drying the mixture for 12 hours, taking out the mixture, and cutting the mixture into pieces to obtain the positive electrode piece.
(8) In the form of LiFeSO4And assembling the positive electrode solid electrolyte lithium sheet into a CR2025 button cell, keeping the temperature of the assembled cell at 50 ℃ for 24h, taking out the assembled cell, and keeping the pressure at 10MPa for 5 min. The charge and discharge test temperature was 50 ℃.
Referring to the charge and discharge curves of fig. 2 and the rate plot of fig. 3, it can be seen that the all-solid-state battery according to the present invention can effectively perform the charge and discharge test at 50 ℃.
Example 2
(1) Preparing a PAA | graphene oxide mixed solution: dispersing 0.17g of 4, 4 '-diaminodiphenyl ether (ODA) into 30mL of Dimethylacetamide (DMAC), adding 0.45g of 4, 4' -diphenyl ether dianhydride (ODPA) under stirring, stirring for 1h, centrifuging at 5000r/min, dropwise adding the obtained bottom layer filtrate into ionized water to generate PAA precipitate, and carrying out cold drying on the precipitate to obtain PAA powder. 0.05g of PAA is dissolved in 1mL of deionized water and 0.01g of Triethylamine (TEA) mixed solvent, and the mixed solvent is uniformly mixed with 20mL of graphene oxide solution.
(2) Based on the consideration of the diameter and the thickness of an electrolyte film, a CR2032 positive shell is selected as a hydrothermal reaction vessel, and the specific operation is as follows: and transferring 500 mu L of graphene oxide mixed solution, obtaining a graphene hydrogel sheet by a hydrothermal method, and directly soaking the hydrogel sheet into the mixed solution of PDMS after cold drying, wherein the PDMS solution comprises the following components in percentage by mass: curing agent: n-hexane 10: 1: weighing 1000 parts by weight, soaking for 6 hours, taking out, heating in a glove box to 60 ℃, and drying to obtain the modified graphene aerogel skeleton.
(3) All reagents used for blending the plasticizer are required to be dried in vacuum at 80 ℃ for 24h, and the components are as follows: FEC: VC is 1: 1: weighing 0.25g, 0.25g and 0.25g of 1 by weight, selecting 2g of acetonitrile as an auxiliary solvent to accelerate dissolution, stirring and reacting in a glove box at 60 ℃ for 2 hours at the rotating speed of 1250r/min, and controlling the temperature of the solution to be about 40 ℃ all the time after the reaction is finished.
(4) PEO (average Mv-300,000) and a LiTFSI reagent used in the electrolyte are dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 1g of PEO, 0.32g of LiTFSI and 7-8 g of acetonitrile, sequentially adding the LiTFSI and the PEO reagent to the acetonitrile under stirring at the rotating speed of 1400r/min, and reacting at room temperature for 24h, wherein the experimental processes are all carried out in a glove box.
(5) Heating all the obtained PEO-based electrolyte precursor to 50 ℃, slowly dripping 0.25g of the blended plasticizer under the stirring condition, rotating at the speed of 600r/min, keeping the temperature at 50 ℃ for 30min after finishing dripping, naturally cooling to room temperature, and stirring for 2 h.
6) And (3) dripping 3-5 ml of electrolyte obtained in the step (5) on a polytetrafluoroethylene plate by using a dropper, naturally soaking for 1h, wiping off redundant electrolyte on the surface by using absorbent cotton, naturally drying for 5h, turning to the back, and repeating the pouring step to obtain the 3D network structure all-solid-state electrolyte with the second set of parameters.
Comparative example 1
(1) All reagents used for blending the plasticizer are required to be dried in vacuum at 80 ℃ for 24h, and the components are as follows: FEC: VC is 2: 1: weighing 0.5g, 0.25g and 0.25g of 1 by weight, selecting 2g of acetonitrile as an auxiliary solvent to accelerate dissolution, stirring and reacting in a glove box at 60 ℃ for 2 hours at the rotating speed of 1250r/min, and controlling the temperature of the solution to be about 40 ℃ all the time after the reaction is finished.
(2) PEO (average Mv-300,000) and a LiTFSI reagent used in the electrolyte are dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding LiTFSI and PEO reagents into the acetonitrile under stirring, wherein the rotation speed is 1400r/min, and reacting at room temperature for 24 hours, wherein the experimental processes are all carried out in a glove box.
(3) Heating all the obtained PEO-based electrolyte precursor to 40 ℃, slowly dripping 0.25g of the blended plasticizer under the stirring condition, rotating at the speed of 600r/min, keeping the temperature at 40 ℃ for 30min after finishing dripping, naturally cooling to room temperature, and stirring for 2 h.
(4) The preparation of the uncomplexed polymer electrolyte is completed on a polytetrafluoroethylene plate, the uncomplexed polymer electrolyte is directly poured by a tape casting method, and the pure polymer solid electrolyte is obtained after natural drying in a glove box for 24 hours, wherein the charge-discharge curve of the battery obtained in the embodiment at 50 ℃ at 0.05C is shown as a curve ① shown in figure 4.
Comparative example 2
(1) Preparing a PAA | graphene oxide mixed solution: dispersing 0.325g of 4, 4 '-diaminodiphenyl ether (ODA) into 30mL of Dimethylacetamide (DMAC), adding 0.583g of 4, 4' -diphenyl ether dianhydride (ODPA) while stirring, stirring for 1h, centrifuging at 5000r/min, dropwise adding the obtained bottom layer filtrate into ionized water to generate PAA precipitate, and carrying out cold drying on the precipitate to obtain PAA powder. 0.054g of PAA is dissolved in 1mL of deionized water and 0.01g of Triethylamine (TEA) mixed solvent, and the mixed solvent is uniformly mixed with 20mL of graphene oxide solution.
(2) Based on the consideration of the diameter and the thickness of an electrolyte film, a CR2032 positive shell is selected as a hydrothermal reaction vessel, and the specific operation is as follows: and (3) transferring 300 mu L of graphene oxide mixed solution, obtaining a graphene hydrogel sheet by a hydrothermal method, and carrying out cold drying on the hydrogel sheet (the cold drying conditions are the same as those in example 1) to obtain the graphene aerogel framework which is not soaked in the PDMS solution.
(3) All reagents used for blending the plasticizer need to be dried in vacuum at 80 ℃ for 24 hours, and the components are as follows: FEC: VC is 2: 1: weighing 0.5g, 0.25g and 0.25g of 1 by weight, selecting 2g of acetonitrile as an auxiliary solvent to accelerate dissolution, stirring and reacting in a glove box at 60 ℃ for 2 hours at the rotating speed of 1250r/min, and controlling the temperature of the solution to be about 40 ℃ all the time after the reaction is finished.
(4) PEO (average Mv-300,000) and a LiTFSI reagent used in the electrolyte are dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding the LiTFSI and the PEO reagent under stirring at the rotating speed of 1400r/min, and reacting at room temperature for 24 hours, wherein the experimental processes are all carried out in a glove box.
(5) Heating all the obtained PEO-based electrolyte precursor to 40 ℃, slowly dripping 0.25g of the blended plasticizer under the stirring condition, rotating at the speed of 600r/min, keeping the temperature at 40 ℃ for 30min after finishing dripping, naturally cooling to room temperature, and stirring for 2 h.
(6) And (3) finishing on a polytetrafluoroethylene plate, dripping 5-10 ml of the obtained electrolyte by using a dropper to the surface of the obtained graphene aerogel sheet, naturally infiltrating for 2 hours, wiping off the redundant electrolyte on the surface by absorbent cotton, naturally drying for 5 hours, turning to the back, and repeating the pouring step to obtain the 3D network structure all-solid-state electrolyte, wherein the charging and discharging curve of the battery at 0.05C at 50 ℃ obtained in the embodiment refers to a curve ② shown in figure 4.
Comparative example 3
(1) Based on the consideration of the diameter and the thickness of an electrolyte film, a CR2032 positive shell is selected as a hydrothermal reaction vessel, and the specific operation is as follows: transferring 300 mu L of pure graphene oxide solution without PAA modification, obtaining a graphene hydrogel sheet by a hydrothermal method, and directly soaking the hydrogel sheet into a mixed solution of PDMS after cold drying (the cold drying condition is the same as that of example 1), wherein the solution comprises the following components in percentage by weight: curing agent: n-hexane 10: 1: weighing 1000 parts by weight, soaking for 6 hours, taking out, heating in a glove box to 60 ℃, and drying to obtain the modified graphene aerogel skeleton.
(2) All reagents used for blending the plasticizer need to be dried in vacuum at 80 ℃ for 24 hours, and the components are as follows: FEC: VC is 2: 1: weighing 0.5g, 0.25g and 0.25g of 1 by weight, selecting 2g of acetonitrile as an auxiliary solvent to accelerate dissolution, stirring and reacting in a glove box at 60 ℃ for 2 hours at the rotating speed of 1250r/min, and controlling the temperature of the solution to be about 40 ℃ all the time after the reaction is finished.
(3) PEO (average Mv-300,000) and a LiTFSI reagent used in the electrolyte are dried in vacuum at 50 ℃ for 48h, acetonitrile is selected as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding the LiTFSI and the PEO reagent under stirring at the rotating speed of 1400r/min, and reacting at room temperature for 24 hours, wherein the experimental processes are all carried out in a glove box.
(4) Heating all the obtained PEO-based electrolyte precursor to 40 ℃, slowly dripping 0.25g of the blended plasticizer under the stirring condition, rotating at the speed of 600r/min, keeping the temperature at 40 ℃ for 30min after finishing dripping, naturally cooling to room temperature, and stirring for 2 h.
(5) And (3) finishing on a polytetrafluoroethylene plate, dripping 5-10 ml of the obtained electrolyte by using a dropper to the surface of the obtained graphene aerogel sheet, naturally infiltrating for 2 hours, wiping off the redundant electrolyte on the surface by absorbent cotton, naturally drying for 5 hours, turning to the back, and repeating the pouring step to obtain the 3D network structure all-solid-state electrolyte, wherein the charging and discharging curve of the battery at 0.05C at 50 ℃ obtained in the embodiment refers to a curve ③ shown in figure 4.
Comparative example 4
With reference to the embodiment of the invention, two plasticizers (PEG and FEC) were mixed in a total amount of 0.5g, in a weight ratio of 1: 1, preparation; other process parameters and raw materials are not changed, and 3D network polymer composite electrolytes with different addition ratios of the plasticizer can be obtained. The charge and discharge curve of the battery obtained in this example at 50 ℃ under 0.05C is shown in FIG. 5.
Comparative example 5
Referring to the specific embodiment of the present invention, step 3 is adjusted as follows-all reagents used for blending plasticizers need to be vacuum dried at 80 ℃ for 24h, and the components are PEG: FEC: VC is 2: 1: 1, 0.5g, 0.25g and 0.25g were taken in this order and added directly to the PEO electrolyte solution described in step 4. Other technological parameters and raw materials are not changed, and the composite electrolyte which is not heated and reacted by the plasticizer can be obtained. The charge and discharge curve of the battery obtained in this example at 50 ℃ under 0.05C is shown in FIG. 6.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A PEO polymer-based 3D network structure all-solid-state electrolyte is characterized in that: the solid electrolyte takes reinforced modified graphene aerogel as a network framework, polyethylene oxide (PEO) as a high polymer matrix, a blending reactant of polyethylene glycol (PEG), fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) as a plasticizer, PEO, lithium bistrifluoromethylsulfonyl imide (LiTFSI) and the plasticizer are blended, and the blending liquid is poured into the modified graphene aerogel to prepare the all-solid electrolyte.
2. A preparation method of a PEO polymer-based 3D network structure all-solid-state electrolyte is characterized by comprising the following steps:
(1) pre-strengthening graphene by using Polyimide (PI) to obtain a graphene oxide mixed solution;
(2) performing secondary reinforcement modification on the graphene aerogel by adopting Polydimethylsiloxane (PDMS);
(3) preparing a blend of PEG, FEC and VC according to the weight ratio, and heating to react to obtain a plasticizer;
(4) weighing PEO and LiTFSI reagents according to the EO/Li ratio and dissolving the PEO and the LiTFSI reagents in an acetonitrile reagent to obtain a precursor solution;
(5) adding the plasticizer in the step (3) into the precursor liquid in the step (4) and blending to obtain a blended liquid;
(6) pouring the blending liquid obtained in the step (5) into the graphene aerogel modified in the step (2) to obtain the novel all-solid-state electrolyte.
3. The method for preparing the PEO polymer-based 3D network structure all-solid-state electrolyte according to claim 2, wherein the pre-strengthening of the graphene in the step (1) comprises the following steps: dispersing 0.1-0.4 g of 4, 4 '-diaminodiphenyl ether (ODA) into 20-50 mL of Dimethylacetamide (DMAC), adding 0.3-0.7 g of 4, 4' -diphenyl ether dianhydride (ODPA) under stirring, stirring for 1h, centrifuging at 5000r/min, dropwise adding the obtained bottom layer filtrate into ionized water to generate PAA precipitate, carrying out cold drying on the precipitate to obtain PAA powder, dissolving 0.03-0.08 g of PAA powder into a mixed solvent of 1mL of deionized water and 0.01g of Triethylamine (TEA), and uniformly mixing 1mL of PAA mixed solution and 20-30 mL of graphene oxide solution to obtain the graphene oxide mixed solution.
4. The preparation method of the PEO polymer-based 3D network structure all-solid-state electrolyte according to claim 2, wherein the secondary reinforced modified graphene aerogel in the step (2) adopts a positive electrode shell of a CR2032 button cell as a reaction vessel, 300 μ L of the graphene oxide mixed solution in the step (1) is transferred, a graphene hydrogel sheet is obtained by a hydrothermal method, and the graphene hydrogel sheet is frozen at-80 ℃ for 10 hours and then vacuumized to-0.1 MPa for freeze drying for 24 hours; directly soaking the obtained aerogel into a PDMS solution for 6h, taking out the aerogel, heating the aerogel in a glove box to 60 ℃, and drying the aerogel to be completely dry to obtain a modified graphene aerogel framework, wherein the PDMS solution is prepared from the following components in percentage by mass: curing agent: n-hexane 10: 1: 1000 parts by weight.
5. The method for preparing a PEO polymer-based 3D network structure all-solid-state electrolyte according to claim 2, wherein the reagents used in step (3) are dried under vacuum at 80 ℃ for 24h, and the ratio of PEG: FEC: VC is 2: 1: weighing 1, selecting 2-4 g acetonitrile as an auxiliary solvent, stirring and reacting for 2 hours in a glove box at 60 ℃, wherein the rotating speed is 1250r/min, and the temperature of the solution is always controlled at 40 ℃ after the reaction.
6. The method for preparing a PEO polymer-based 3D network-structured all-solid electrolyte according to claim 2, wherein the PEO and LiTFSI used in the step (4) are dried under vacuum at 50 ℃ for 48 hours, acetonitrile is used as a solvent, and the ratio of EO/Li is 20: 1, respectively weighing 0.5g of PEO, 0.163g of LiTFSI and 3.5g of acetonitrile, sequentially adding LiTFSI and PEO reagents into the acetonitrile under stirring, rotating at 1400r/min, and reacting at room temperature for 24 h.
7. The preparation method of the PEO polymer-based 3D network structure all-solid-state electrolyte as claimed in claim 2, wherein in the solution mixing process in the step (5), the addition amount of the plasticizer accounts for 10-20% of the total mass of PEO and lithium salt, the precursor solutions obtained in the steps (3) and (4) need to be controlled at 40 ℃, the plasticizer in the step (3) is dropwise added into the PEO precursor electrolyte in the step (4) while stirring, the rotation speed is 600r/min, after the dropwise addition is completed, the temperature is kept at 40 ℃ for 30min, and then the mixture is naturally cooled to room temperature and stirred for 2 h.
8. The preparation method of the 3D network structure all-solid-state electrolyte according to claim 2, wherein the pouring process in the step (6) is completed on a polytetrafluoroethylene plate, an excessive amount of the electrolyte obtained in the step (5) is dripped by a dropper to the surface of the graphene aerogel sheet obtained in the step (2), the graphene aerogel sheet is naturally soaked for 2 hours, the excessive electrolyte on the surface is wiped off by absorbent cotton, the graphene aerogel sheet is naturally dried for 5 hours and turned over to the back, and the pouring step is repeated, so that the 3D network structure all-solid-state electrolyte is obtained.
9. The application of the 3D network structure all-solid-state electrolyte according to claim 1, wherein the all-solid-state electrolyte is used for button type all-solid-state lithium ion batteries, a lithium sheet is selected as a negative electrode, and the distribution ratio of a positive electrode sheet group is LiFePO4: (superP: acetylene black): (PVDF: electrolyte precursor) 7: (0.5:0.5): (1: 1), manually grinding the positive electrode precursor until a mirror surface effect is presented, smearing a smear on an aluminum foil by using a scraper with scales of 150 microns, standing for 2 hours in vacuum, heating to 60 ℃, drying for 12 hours, taking out, and cutting into pieces to obtain a positive electrode piece; CR2025 button cells were assembled with positive | solid state electrolyte | lithium sheets.
10. The application of the 3D network structure all-solid-state electrolyte according to claim 9, wherein the battery needs to be kept at 50 ℃ for 24h, then taken out and kept at 10MPa for 5min for testing, and the charging and discharging test temperature is 50 ℃.
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