CN114006029B - Solid electrolyte and solid battery containing same - Google Patents
Solid electrolyte and solid battery containing same Download PDFInfo
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Abstract
The invention discloses a solid electrolyte and a solid battery containing the electrolyte, wherein a novel polymer material (crown ether organic covalent framework structure materials (COFs)) is synthesized to be used as a modification layer to modify two sides of an inorganic solid electrolyte and/or an organic solid electrolyte in situ, and the final solid battery structure is a sandwich-type structure of 'positive plate-polymer-inorganic solid electrolyte and/or organic solid electrolyte-polymer-negative plate'. The modification method can effectively improve the interface performance between the solid electrolyte and the electrode in situ, and the prepared polymer solid electrolyte coating can remarkably increase the transmission channel of lithium ions at the interface of the positive electrode/the inorganic ceramic sheet/the negative electrode so as to reduce the transmission impedance of the solid-solid interface, protect the inorganic solid electrolyte and/or the organic solid electrolyte from being reduced by the metal lithium negative electrode and improve the electrochemical performance of the solid battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a solid electrolyte for improving interface performance, a preparation method thereof and a solid battery containing the solid electrolyte.
Background
The traditional lithium ion battery adopts inflammable liquid electrolyte and graphite as a negative electrode, so that the energy density is not high, and potential safety hazards also exist. Solid-state batteries have received much attention in next-generation energy storage devices due to their higher energy density and superior safety performance compared to the most advanced lithium ion batteries at present.
However, after the electrolyte is changed from a liquid state to a solid state, the solid-liquid interface of the electrode material-electrolyte in the lithium battery system is transformed to the solid-solid interface of the electrode material-solid electrolyte, the solid-solid interfaces have no wettability, and the transmission of ions is seriously affected by the interface contact resistance, so that the internal resistance of the all-solid-state lithium ion battery is sharply increased, and the cycle performance and the rate performance of the battery are both poor. In addition, the solid electrolyte has a problem of poor compatibility with an interface between electrodes, and also has a problem that the interface is easily separated due to volume expansion and contraction of each material during charge and discharge.
Adopt solid electrolyte to replace electrolyte and diaphragm, can simplify the equipment process and the cost of battery to a very big extent, solid electrolyte mainly can divide into: oxide solid electrolytes, sulfide solid electrolytes, polymer solid electrolytes, and composite solid electrolytes. Wherein the oxide solid electrolyte has high lithium ion conductivity (10) -4 S/cm-10 -3 S/cm) and has better air stability, so the preparation and the preservation of the compound do not need the protection of inert atmosphere, and the compound has good development prospect. Oxide solid electrolytes are of the NASICON type (LATP, LAGP); garnet type (LLZO, LLZTO, etc.) solid electrolytes are representative, and due to their hard characteristics, interface impedance is large when directly contacting and assembling positive and negative electrode sheets, and lithium ions cannot smoothly pass through positive/electrolyte and electrolyte/negative electrode interfaces during charging and discharging, thereby seriously affecting the electrochemical performance of solid lithium batteries. Particularly, the lithium metal negative electrode and the garnet-type solid electrolyte surface do not wet each other, so that a large interface resistance exists between the electrode material and the solid electrolyte material, and the electrode material and the garnet-type solid electrolyte material cannot be assembled into a high-performance all-solid-state lithium ion battery. The organic polymer solid electrolyte can greatly improve interface contact sites, reduce interface impedance and increase a transmission channel of lithium ions at an interface due to the flexible characteristic of the organic polymer solid electrolyte when the organic polymer solid electrolyte is in contact with a positive electrode and a negative electrode, so that the organic polymer solid electrolyte is extremely beneficial to improving the electrochemical performance of a battery. Oxide solid state powerThe use of a suitable polymer modification layer between the electrolyte and the lithium metal negative electrode to improve the interface problem and suppress the occurrence of side reactions is becoming a viable strategy to improve electrochemical performance.
Therefore, there is a need to develop a polymer solid electrolyte coating that can improve the interfacial properties between the solid electrolyte and the electrode in situ, has strong ionic conductivity and considerable cohesiveness, so as to improve the interfacial wettability between the solid electrolyte and the lithium metal electrode while utilizing the excellent properties of the oxide solid electrolyte, thereby fundamentally realizing high safety, high reliability and long life energy storage.
Disclosure of Invention
In order to improve the technical problem, the present invention provides a novel synthetic polymer material (crown ether organic covalent framework materials (COFs)) as a modification layer to modify both sides of an inorganic solid electrolyte and/or an organic solid electrolyte in situ. The method can obviously increase the transmission channel of lithium ions at the interface of the positive electrode/the solid electrolyte/the negative electrode so as to reduce the transmission impedance of the solid-solid interface and protect the solid electrolyte from being reduced by the metal lithium negative electrode, thereby improving the electrochemical performance of the solid battery.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a modification layer of a solid electrolyte, which comprises a polymer with a crown ether organic covalent skeleton structure.
According to the invention, the polymer has the structure shown in the following formula I:
formula I
Wherein: n ≧ 1 and is an integer, e.g., n =1, 2, 3.
According to the invention, the modification layer is prepared by in-situ polymerization of a precursor, wherein the precursor comprises 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (4, 4',4' ',4' '' - (pyrene-1,3,6,8-tetrayl) tetra aniline) and a monomer with a structure shown in a formula II:
formula II
Wherein: n ≧ 1 and is an integer, e.g., n =1, 2, 3.
According to exemplary embodiments of the invention, the monomer of formula II may be selected from
、
And the like.
The invention also provides a preparation method of the modification layer of the solid electrolyte, which comprises the step of reacting 1,3,6, 8-tetra- (p-aminophenyl) -pyrene with a monomer with a structure shown in the formula II to prepare the modification layer.
According to the invention, the monomers of the structure of formula II have the definitions as described above.
According to the invention, the molar ratio of the 1,3,6, 8-tetra- (p-aminophenyl) -pyrene to the monomer having the structure shown in formula II is 1 (0.5-2), and is exemplarily 1:0.5, 1:1, 1: 2.
According to the invention, the 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and the monomer with the structure shown in the formula II are added into the reaction system in the form of solution. For example, a solution of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene in o-dichlorobenzene and a solution of structural monomer represented by formula II in acetic acid are prepared separately, and the two solutions are mixed to obtain a mixed solution.
According to the invention, the temperature of the reaction is 40-60 ℃, exemplary 40 ℃, 50 ℃, 60 ℃; further, the reaction time is not less than 12 hours, and is exemplified by 24 hours.
According to the present invention, the preparation method further comprises washing the product after the polymerization reaction. For example, the solvent for the washing may be tetrahydrofuran.
According to the present invention, the preparation method further comprises drying the washed product to remove the residual solvent. For example, the drying temperature may be 40 to 60 ℃, and exemplary temperatures are 40 ℃, 50 ℃, and 60 ℃.
According to the invention, the preparation method also comprises the step of carrying out crystal form transformation on the dried product. For example, the solvent used for the crystal form transformation is a mixed solvent of o-dichlorobenzene and n-butanol.
According to an exemplary embodiment of the present invention, the mixed solvent has a mixed volume ratio of ortho-dichlorobenzene and n-butanol of (5-10):1, exemplary 5:1, 6:1, 7:1, 8:1, 9:1, 10: 1.
According to an exemplary embodiment of the present invention, the crystal form transformation is further performed by a catalyst. For example, the catalyst may be at least one of pyrrolidine, polyvinylpyrrolidone, 3-pyrrolidinol, 2-pyrrolidinone, and the like. For another example, the amount of the catalyst is 5 to 10% of the amount of the mixed solvent, and is exemplarily 5%, 8%, 10%.
According to an exemplary embodiment of the invention, the temperature of the crystal form transformation is 40 to 60 ℃, exemplary 40 ℃, 50 ℃, 60 ℃; further, the time for the crystal form transformation is not less than 24h, illustratively 72 h.
According to the invention, the preparation method specifically comprises the following steps:
1) dissolving 1,3,6, 8-tetra- (p-aminophenyl) -pyrene in o-dichlorobenzene, and stirring to dissolve;
2) dissolving a monomer with a structure shown in a formula II in acetic acid, adding the monomer into the solution obtained in the step 1), and stirring for reaction;
3) after the reaction is finished, washing and drying a reaction product;
4) and (4) carrying out crystal form transformation on the product obtained in the step (3) to obtain a modification layer of the solid electrolyte.
The invention also provides application of the modification layer of the solid electrolyte in the solid electrolyte.
The invention also provides a solid electrolyte which contains the modification layer of the solid electrolyte.
According to the invention, the solid electrolyte comprises an inorganic solid electrolyte and/or an organic solid electrolyte, and a modification layer positioned on at least one side surface of the inorganic solid electrolyte and/or the organic solid electrolyte, wherein the modification layer is the modification layer of the solid electrolyte.
According to the invention, the width of the modification layer is larger than that of the battery pole piece, and preferably the width of the modification layer is at least about 5 μm larger than that of the battery pole piece.
According to the present invention, the inorganic solid electrolyte includes, but is not limited to, at least one of NASICON-type solid electrolyte, perovskite-type solid electrolyte, sulfide-type solid electrolyte, garnet-type solid electrolyte.
According to the invention, the NASICON-type solid electrolyte includes, but is not limited to, LiTi 2 (PO 4 ) 3 、Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 And Li 1.4 Al 0.4 Ti 1.4 Ge 0.2 (PO 4 ) 3 At least one of (1).
According to the present invention, the perovskite-type solid electrolyte includes, but is not limited to, Li 0.34 La 0.51 TiO 2.94 、Li 0.34 Nd 0.55 TiO 3 、(Li 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01 O 3 And Li 3x La 2/3-x TiO 3 (x ≈ 0.10).
According to the present invention, the garnet-type solid electrolyte includes, but is not limited to, Li 3 Ln 3 Ta 2 O 12 、Li 7 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 And Li 6.5 La 3 Zr 1.75 Te 0.25 O 12 At least one of (1).
According to the present invention, the sulfide solid state electrolyte includes, but is not limited to, Li 2 S-SiS 2 Sulfide binary System, Li 2 S-P 2 S 5 A sulfide binary system and at least one of the products of doped substitution of the two sulfide binary systems.
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
the modification layer is prepared on at least one side surface of the inorganic solid electrolyte and/or the organic solid electrolyte in situ by the preparation method of the modification layer of the solid electrolyte.
According to the present invention, the inorganic solid electrolyte and/or the organic solid electrolyte may also be pretreated before the reaction. For example, it is subjected to a sanding pretreatment using 400-mesh and 2000-mesh sandpaper in order, and then impurities on the surface are washed off with an anhydrous tetrahydrofuran solvent.
According to the present invention, the method for preparing the solid electrolyte comprises the steps of:
s1: polishing the surface of the inorganic solid electrolyte and/or the organic solid electrolyte in a glove box filled with argon, washing by using an anhydrous tetrahydrofuran solvent and drying by blowing;
s2: placing the inorganic solid electrolyte and/or the organic solid electrolyte pretreated in the step S1 into an o-dichlorobenzene solution of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (4, 4',4' ',4' '' - (pyrene-1,3,6, 8-tetra-yl) tetra-aniline), and stirring for reaction;
s3, adding an acetic acid solution of the monomer with the structure shown in the formula II into the solution, and stirring for reacting for 24 hours;
s4: washing off unreacted residues by using anhydrous tetrahydrofuran, and drying to remove residual solvent;
s5: and (4) adding the product prepared in the step (S4) into a crystallization transformation solvent consisting of o-dichlorobenzene and n-butanol, adding a catalyst at the same time, and reacting to obtain the solid electrolyte.
According to the invention, in step S2, the reaction temperature is 40-60 ℃, exemplary 40 ℃, 50 ℃, 60 ℃; further, the reaction time is 0.5-2 h, and is exemplified by 0.5h, 1h and 2 h.
According to the invention, in step S3, the temperature of the reaction is 40-60 ℃, exemplary 40 ℃, 50 ℃, 60 ℃; further, the reaction time is not less than 12 hours, and is exemplified by 24 hours.
According to the present invention, in step S5, the mixing volume ratio of o-dichlorobenzene and n-butanol in the mixed solvent is (5-10):1, exemplary 5:1, 6:1, 7:1, 8:1, 9:1, 10: 1.
According to the present invention, in step S5, the crystal form transformation is performed under the action of a catalyst. For example, the catalyst may be at least one of pyrrolidine, polyvinylpyrrolidone, 3-pyrrolidinol, 2-pyrrolidinone, and the like. For another example, the amount of the catalyst is 5 to 10% of the amount of the mixed solvent, and is exemplarily 5%, 8%, 10%.
According to the invention, in step S5, the temperature of the crystal form transformation is 40 to 60 ℃, exemplary 40 ℃, 50 ℃, 60 ℃; further, the time for the crystal form transformation is not less than 24h, illustratively 72 h.
The invention also provides the application of the solid electrolyte in a battery.
According to the present invention, the battery may be at least one of a secondary battery (e.g., various types of ion secondary batteries such as lithium, sodium, magnesium, aluminum, zinc, etc.), a solid-state battery (e.g., all-solid-state battery, quasi-solid-state battery), a gel battery, a liquid battery, or the like.
The invention also provides a battery comprising the solid electrolyte.
According to the present invention, the battery further includes a positive electrode tab and a negative electrode tab respectively located on both sides of the solid electrolyte.
Preferably, the positive active material of the positive electrode sheet includes, but is not limited to, layered LiCoO 2 、LiNiO 2 And LiNi x Co 1-x O 2 Ternary positive electrode material (e.g. LiNi) 1/3 Mn 1/3 Co 1/3 O 2 And LiNi 0.85 Co 0.1 Al 0.05 O 2 ) Spinel LiMn 2 O 4 5V spinel LiNi 0.5 Mn 1.5 O 4 Phosphate LiMPO 4 (M ═ Fe, Mn), lithium-rich manganese-based positive electrode materialLi[Li x (MnM) 1-x ]O 2 (M ═ Ni, Co, Fe), and sulfur electrodes.
Preferably, the negative active material of the negative electrode sheet includes, but is not limited to, metallic lithium, lithium alloy Li x M (M ═ In, B, Al, Ga, Sn, Si, Ge, Pb, As, Bi, Sb, Cu, Ag, Zn), carbon-based material (graphite, amorphous carbon, mesocarbon microbeads), silicon-based material (silicon-carbon material, nano silicon), tin-based material, and lithium titanate (Li) (Li ═ In, B, Al, Ga, Sn, Si, Ge, Pb, As), carbon-based material (graphite, amorphous carbon, mesocarbon microbeads), silicon-based material (silicon-carbon material, nano silicon), tin-based material, and lithium titanate 4 Ti 5 O 12 ) And the like.
The invention also provides a preparation method of the battery, which comprises the steps of modifying the precursor on at least one side surface of the inorganic solid electrolyte and/or the organic solid electrolyte, and respectively placing the positive plate and the negative plate on two sides of the coated inorganic solid electrolyte and/or organic solid electrolyte to assemble the battery.
The invention has the beneficial effects that:
the solid battery interface modification material takes crown ether COFs as a modification layer to modify the two sides of an inorganic solid electrolyte and/or an organic solid electrolyte in situ, and the final solid battery structure is a sandwich-type structure of 'positive plate-polymer-inorganic solid electrolyte and/or organic solid electrolyte-polymer-negative plate'. The modification method can effectively improve the interface performance between the solid electrolyte and the electrode in situ, and the prepared polymer solid electrolyte coating can remarkably increase the transmission channel of lithium ions at the interface of the positive electrode/the inorganic ceramic sheet/the negative electrode so as to reduce the transmission impedance of the solid-solid interface, protect the inorganic solid electrolyte and/or the organic solid electrolyte from being reduced by the metal lithium negative electrode and improve the electrochemical performance of the solid battery. Compared with other modification strategies, the method has the characteristic of strong universality and can be suitable for almost all anode and cathode materials at present.
(1) The key point of the modification method is that the modification strategy adopts an inorganic solid electrolyte and/or organic solid electrolyte in-situ growth method, and the crown ether COFs is obtained by adding an additive into a reaction system of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (4, 4',4' ',4' '' - (pyrene-1,3,6,8-tetrayl) tetra-aniline) and o-dichlorobenzene solution. The prepared electrode pole pieces are arranged on two sides of the solid electrolyte, and the crown ether COFs modification layer is tightly contacted with the electrode material by pressurization, so that the solid electrolyte is more firmly contacted with an electrode interface, the problem of poor contact between the solid electrolyte and the electrode interface is further solved, and the electrode material deformation in the battery circulation process is bound to a certain extent.
(2) The crown ether COFs of the solidified polymer solid electrolyte coating has rich lithium ion migration sites, so that the crown ether COFs modified solid electrolyte has excellent ionic conductivity which is up to 1.2 mS/cm.
(3) The solidified polymer solid electrolyte coating crown ether COFs has better cohesiveness and better interface wettability; after the assembled solid-state battery applies pressure, the solid-state electrolyte is contacted with the electrode interface more firmly, so that the problem of poor interface contact between the solid-state electrolyte and the electrode is further solved, and the deformation of an electrode material in the battery circulation process is bound to a certain extent.
(4) The solidified polymer solid electrolyte coating COFs has better chemical stability and electrochemical stability due to the three-dimensional cross-linked structure.
(5) The COFs of the solidified polymer solid electrolyte coating can be applied to various all-solid-state ion secondary batteries of lithium, sodium, magnesium, aluminum, zinc and the like by adjusting parameters of different solvents, additives, inorganic salts and the like.
(6) The solid electrolyte has the advantages of simple preparation process, high yield and low cost, is suitable for industrial application, and has wide application prospect in the fields of portable electronic equipment and power batteries.
Drawings
Fig. 1 is a schematic structural view of a solid-state battery of the present invention; in the figure: 1. a positive plate; 2. a solid electrolyte; 3. a negative plate; 4. COFs modifying layer.
Fig. 2 is a graph showing the cycle performance of the solid-state battery of the present invention.
FIG. 3 is a flowchart of the preparation of COFs-1, which is a precursor for modifying a solid electrolyte in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The invention is further illustrated by the following specific examples.
The test method comprises the following steps:
ionic conductivity test of crown ether COFs polymer solid electrolyte: assembling a steel sheet | coating | steel sheet battery by using a CR2032 coin cell assembly, testing by using a Chenghua 660E electrochemical workstation, obtaining the impedance (R/omega) of an electrolyte membrane (crown ether COFs) by an EIS alternating current impedance testing method, and measuring the thickness (d/cm) and the area (S/cm) of the electrolyte membrane 2 ) Using the formula
Calculating to obtain the ionic conductivity (sigma/s cm) -1 ）。
Testing the internal resistance of the battery: after the solid-state battery is assembled, testing by using a Chenghua 660E electrochemical workstation, and obtaining the internal resistance of the solid-state battery by an EIS alternating-current impedance testing method.
And (3) testing the cycle number of the battery: after the solid-state battery is assembled, a LAND blue battery test system is used for carrying out cycle performance test under the conditions of 0.2C/0.2C charge-discharge current and 3.0V-4.4V charge-discharge voltage.
And (3) testing the peel strength: and clamping the assembled solid-state battery by using a universal tensile testing machine, and then testing.
Example 1
Preparing crown ether COFs-1:
s1: LLZTO (Li) having a thickness of 100 μm was sanded in an argon-filled glove box using 400 mesh and 2000 mesh sandpaper, respectively 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ) Removing residual impurities on the surface of the electrolyte by using an anhydrous tetrahydrofuran solvent;
s2: placing the clean LLZTO electrolyte treated in the step S1 into a reaction flask containing 0.024 mmol of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and 10 mL of o-dichlorobenzene solution, and stirring at 50 ℃ for 1 h;
s3: adding 0.024 mmol of
And 0.1mL of 6M acetic acid solution, and stirring the mixture at 50 ℃ to react for 24 hours;
S4: washing off unreacted residues by using anhydrous tetrahydrofuran, and heating for 1 h at the temperature of 50 ℃ to remove residual solvent;
s5: to the COF @ LLZTO material prepared in step S4, a crystallization-converting solvent consisting of 13.5 mL of o-dichlorobenzene and 1.5 mL of n-butanol was added, and at the same time, 1.5 mL of pyrrolidine was added as a catalyst. Then, the reaction system is kept at 50 ℃, and the covalent organic framework material modified LLZTO electrolyte with optimized COF (structure shown in figure 3) crystal form is obtained after three days of reaction.
Preparing a positive electrode material: carbon black is used as a conductive agent, PVDF is used as a binder, and the mixture is uniformly stirred and then added with a positive electrode active material lithium cobaltate to prepare positive electrode active layer slurry (in the mixture, the solid components comprise 90 wt.% lithium cobaltate, 5wt.% binder PVDF and 5wt.% conductive carbon black). And coating the positive active layer slurry on an aluminum foil current collector with the thickness of 13 mu m to prepare the positive pole piece.
Preparing a solid-state battery: as shown in fig. 1, lithium metal was used as a negative electrode (50 μm), melted at 200 ℃, and then coated on one surface of the solid electrolyte obtained in the above step S5, and the above positive electrode sheet (80 μm) was placed on the other surface of the solid electrolyte obtained in the step S5, and a solid lithium battery was assembled and packaged in a coin cell case (CR 2032).
The performance of the solid electrolyte obtained in this example and the performance of the solid-state battery were measured, and the results of the measurements are shown in table 1 and fig. 2.
Example 2
Preparing crown ether COFs-2:
s1: LLZTO (Li) having a thickness of 100 μm was sanded in an argon-filled glove box using 400 mesh and 2000 mesh sandpaper, respectively 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ) Removing possible residual impurities on the surface of the electrolyte by using an anhydrous tetrahydrofuran solvent;
s2: placing the clean LLZTO electrolyte treated in the step S1 into a reaction bottle containing 0.024 mmol of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and 10 mL of o-dichlorobenzene solution, and stirring for 1h at 50 ℃;
s3: adding 0.024 mmol of
And 0.1mL of 6M acetic acid solution, and stirring the mixture at 50 ℃ to react for 24 hours;
s4: washing off unreacted residues by using anhydrous tetrahydrofuran, and heating for 1h at the temperature of 50 ℃ to remove residual solvent;
s5: to the COF @ LLZTO material prepared in step S4, a crystallization-converting solvent consisting of 13.5 mL of o-dichlorobenzene and 1.5 mL of n-butanol was added, and at the same time, 1.5 mL of pyrrolidine was added as a catalyst. And then, keeping the reaction system at 50 ℃, and reacting for three days to obtain the COF crystal form optimized covalent organic framework material modified LLZTO electrolyte.
Preparing a positive electrode material: carbon black is used as a conductive agent, PVDF is used as a binder, and the mixture is uniformly stirred and then added with a positive electrode active material lithium cobaltate to prepare positive electrode active layer slurry (in the mixture, the solid components comprise 90 wt.% lithium cobaltate, 5wt.% binder PVDF and 5wt.% conductive carbon black). And coating the positive active layer slurry on an aluminum foil current collector with the thickness of 13 mu m to prepare the positive pole piece.
Preparing a solid-state battery: as shown in fig. 1, lithium metal was used as a negative electrode (50 μm), melted at 200 ℃, and then coated on one surface of the solid electrolyte obtained in the above step S5, and the above positive electrode sheet (80 μm) was placed on the other surface of the solid electrolyte obtained in the step S5, and a solid lithium battery was assembled and packaged in a coin cell case (CR 2032).
The performance of the solid electrolyte obtained in this example and the performance of the solid-state battery were measured, and the results of the measurements are shown in table 1 and fig. 2.
Comparative example
Preparation of PEO coating materials:
(1) dissolving 0.6g of PEO and 0.13g of SN in 28g of anhydrous acetonitrile solvent, and stirring for 6 hours in a nitrogen environment;
(2) 0.1g of lithium bistrifluoromethylsulphonylimide (LiTFSI) was added and stirring was continued for 24h to give a gummy product.
Preparing a positive electrode material: carbon black is used as a conductive agent, PVDF is used as a binder, and the mixture is uniformly stirred and then added with a positive electrode active material lithium cobaltate to prepare positive electrode active layer slurry (in the mixture, the solid components comprise 90 wt.% lithium cobaltate, 5wt.% binder PVDF and 5wt.% conductive carbon black). And coating the positive active layer slurry on an aluminum foil current collector with the thickness of 13 mu m to prepare the positive pole piece.
Preparing a solid-state battery: as shown in FIG. 1, metallic lithium was used as a negative electrode (50 μm), and the above-mentioned positive electrode tab (80 μm) and LLZTO (Li) 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ) Ceramic solid electrolyte (50 μm) (LLZTO electrolyte coated with 0.2g/cm on both side surfaces 2 PEO coating material) to assemble a solid-state lithium battery, and the positive electrode, the solid-state electrolyte and the negative electrode are sequentially stacked. The solid state cell was left to stand for 2h and then heated at 60 ℃ for 24h to fully cure the PEO. The common tab and the aluminum plastic film sealing material are assisted to assemble the solid lithium battery.
Table 1 table of performance test data of solid electrolyte and solid battery
From the comparison of the comparative examples in table 1 with the results of examples 1, 2, it can be seen that: the crown ether COFs cross-linked polymer coating prepared by the invention has more remarkable advantages in mechanical property, electrochemical property and battery cycle performance compared with the traditional polymer solid electrolyte.
As can be seen from examples 1 and 2 in table 1, the bonding strength of crown ether COFs has a positive correlation with the battery thickness variation during battery cycling, and thus the problem of cycling deformation of the solid-state battery can be effectively improved, which is of great significance for improving the solid-state battery.
From the cycle performance results of the solid-state battery of fig. 2, it can be seen that the cycle performance of the solid-state battery prepared from the COFs-2 modified solid-state electrolyte prepared in example 2 is the best, which can reach 1400 cycles. The above results also agree with the results of the ionic conductivity test. Thereby further proving that the crown ether COFs have remarkable effect on improving the interface performance between the solid electrolyte and the electrode in the solid-state battery.
In conclusion, the crown ether COFs disclosed by the invention not only have stronger chemical properties and electrochemical properties, but also have in-situ curing and excellent mechanical properties, so that the crown ether COFs have important significance for improving the interface performance of the solid-state battery and the overall safety and cycle performance of the solid-state battery.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. A modification layer of a solid electrolyte, which is characterized in that the modification layer comprises a polymer with a crown ether organic covalent skeleton structure, and the polymer has a structure shown as the following formula I:
formula I
Wherein: n is not less than 1 and is an integer.
2. The modified layer of a solid electrolyte of claim 1, wherein the modified layer is prepared by in situ polymerization of a precursor comprising 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and a monomer of formula ii:
formula II
Wherein: n is not less than 1 and is an integer.
3. The modified layer of solid electrolyte of claim 2, wherein the monomer of formula ii is selected from the group consisting of
、
At least one of (1).
4. A solid electrolyte comprising a modification layer of the solid electrolyte according to any one of claims 1 to 3.
5. The solid electrolyte according to claim 4, wherein the solid electrolyte comprises an inorganic solid electrolyte and/or an organic solid electrolyte, and a modification layer provided on at least one surface of the inorganic solid electrolyte and/or the organic solid electrolyte, wherein the modification layer is a modification layer of the solid electrolyte according to any one of claims 1 to 3.
6. The solid state electrolyte of claim 5, wherein the modification layer has a width greater than a width of the battery pole piece.
7. The solid-state electrolyte of claim 5, wherein the inorganic solid-state electrolyte comprises at least one of, but not limited to, a NASICON-type solid-state electrolyte, a perovskite-type solid-state electrolyte, a sulfide solid-state electrolyte, and a garnet-type solid-state electrolyte.
8. The solid electrolyte of claim 7, wherein the NASICON type solid electrolyte includes, but is not limited to, LiTi 2 (PO 4 ) 3 、Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 And Li 1.4 Al 0.4 Ti 1.4 Ge 0.2 (PO 4 ) 3 At least one of (1).
9. The solid state electrolyte of claim 7, wherein the perovskite-type solid state electrolyte includes, but is not limited to, Li 0.34 La 0.51 TiO 2.94 、Li 0.34 Nd 0.55 TiO 3 、(Li 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01 O 3 And Li 3x La 2/3-x TiO 3 (x ≈ 0.10).
10. The solid-state electrolyte of claim 7, wherein the garnet-type solid-state electrolyte includes but is not limited to Li 3 Ln 3 Ta 2 O 12 、Li 7 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 And Li 6.5 La 3 Zr 1.75 Te 0.25 O 12 At least one of (1).
11. The solid-state electrolyte of claim 7, wherein the sulfide solid-state electrolyte includes, but is not limited to, Li 2 S-SiS 2 Sulfide binary System, Li 2 S-P 2 S 5 A sulfide binary system and at least one of the products of doped substitution of the two sulfide binary systems.
12. A battery comprising a solid-state electrolyte according to any one of claims 4 to 11.
13. The battery of claim 12, further comprising positive and negative plates on opposite sides of the solid state electrolyte, respectively.
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