CN114583258B - Polymer electrolyte membrane and preparation method and application thereof - Google Patents
Polymer electrolyte membrane and preparation method and application thereof Download PDFInfo
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- CN114583258B CN114583258B CN202210451854.6A CN202210451854A CN114583258B CN 114583258 B CN114583258 B CN 114583258B CN 202210451854 A CN202210451854 A CN 202210451854A CN 114583258 B CN114583258 B CN 114583258B
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Abstract
The polymer electrolyte membrane comprises a packaging structure connected with a lithium-containing negative electrode in a chemical bond mode, and a solid electrolyte, a silicon-based compound and a high-concentration electrolyte which are filled in the packaging structure; the packaging structure is obtained by crosslinking tin-containing Lewis acid and a polymerization monomer; the polymeric monomer is capable of undergoing a crosslinking reaction with a tin-containing lewis acid. According to the polymer electrolyte membrane, the solid electrolyte, the silicon-based compound and the high-concentration electrolyte are encapsulated inside the encapsulation structure, so that direct contact with lithium metal is avoided, and the conductivity and the oxidation resistance of the polymer electrolyte membrane are improved; in addition, the packaging structure can be connected with the lithium-containing negative electrode in a chemical bond mode, and the unstable state of the interface of the packaging structure and the lithium metal is avoided.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a polymer electrolyte membrane and a preparation method and application thereof.
Background
Lithium metal has a very high theoretical specific capacity (3860 mAh -1 ) And poleThe low potential (-3.040V) when applied to the negative electrode of a lithium battery greatly increases the energy density of the battery. However, lithium metal has high reactivity in an electrolyte system, and particularly, an unstable interface reaction is generated at an electrolyte/lithium metal interface, even lithium dendrites are formed, and then a battery diaphragm is pierced to cause short circuit of a positive electrode and a negative electrode, so that the battery fails and even explodes.
Currently, a solution to the above problem is to use a solid electrolyte membrane, which can prevent lithium metal from reacting with the electrolyte. However, the solid electrolyte membrane is oxidized when the voltage is higher than 4V, so that the solid membrane is damaged, and the protection effect is ineffective; in general, the solid electrolyte has a lower conductivity than the electrolyte, and further causes severe polarization of the battery, and thus normal charge and discharge cycles cannot be maintained. Also, if a pure inorganic solid electrolyte membrane is used, since the interface with the electrode surface is poor, an electrolyte solution needs to be added to solve the problem of poor interface contact, which, however, may cause side reactions to occur.
The conductivity and oxidation resistance of the solid electrolyte membrane are improved, and the stable circulation of the lithium metal battery under a wider electrochemical window can be improved. Therefore, it is still a challenge to obtain a solid electrolyte membrane with high conductivity and oxidation resistance and ensure a good interface between the solid electrolyte membrane and lithium metal without affecting the energy density of the lithium metal battery.
Disclosure of Invention
In view of the above-mentioned limitations, the present application provides a polymer electrolyte membrane; by forming an encapsulation structure, the solid electrolyte, the silicon-based compound and the high-concentration electrolyte are encapsulated inside the encapsulation structure, so that direct contact with lithium metal is avoided, and the conductivity and the oxidation resistance of the polymer electrolyte membrane are improved; in addition, the packaging structure can be connected with the lithium-containing negative electrode in a chemical bond mode, so that the unstable state of the interface with metal lithium is avoided, and the defects in the background art can be overcome.
In order to achieve the purpose, the following technical scheme is adopted in the application:
the invention of the application provides a polymer electrolyte membrane, which comprises a packaging structure connected with a lithium-containing negative electrode in a chemical bond mode, and a solid electrolyte, a silicon-based compound and a high-concentration electrolyte which are filled in the packaging structure; the packaging structure is obtained by crosslinking tin-containing Lewis acid and a polymerization monomer; the polymeric monomer is capable of undergoing a crosslinking reaction with a tin-containing lewis acid.
Optionally, the chemical bond comprises at least one of a covalent bond, a metallic bond, an ionic bond. Optionally, the polymer electrolyte membrane comprises: 25-89 parts by mass of a packaging structure; 1-33 parts of solid electrolyte; 2-47 parts of a silicon-based compound; 2-57 parts of high-concentration electrolyte.
Optionally, the number of the packaging structures can be any number between 25 parts and 89 parts.
Alternatively, the fraction of the solid electrolyte may be any value between 1 part and 33 parts.
Alternatively, the part of the silicon-based compound may be any value between 2 parts and 47 parts.
Alternatively, the part of the high-concentration electrolyte may be any value between 2 parts and 57 parts.
Optionally, the polymer electrolyte membrane comprises: 25-80 parts of a packaging structure; 1-30 parts of a solid electrolyte; 2-40 parts of a silicon-based compound; 2-50 parts of high-concentration electrolyte.
Optionally, the polymer electrolyte membrane comprises: 25-60 parts of a packaging structure; 1-20 parts of a solid electrolyte; 2-30 parts of a silicon-based compound; 2-40 parts of high-concentration electrolyte.
Alternatively, the polymerized monomer comprises a polyhydroxy glyceryl ether compound.
Optionally, the polyhydroxyl glycerol ether compound comprises at least one of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether.
Optionally, the mass ratio of the tin-containing lewis acid to the polymerized monomer is: (0.001-0.1) and (25-89). That is, the tin-containing lewis acid may be selected from 0.001 parts, 0.002 parts, 0.003 parts, 0.004 parts, 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, or any number between any two of these values; the polymerized monomer can be selected from any value of 25-89 parts.
Optionally, the tin-containing lewis acid comprises SnCl 4 、SnCl 2 、Sn(OTF) 2 At least one of (1).
Wherein, Sn (OTF) 2 Is tin trifluoromethanesulfonate.
Optionally, the solid state electrolyte comprises at least one of a sulfide ceramic, a polyphosphate type ceramic, garnet lithium lanthanum zirconium oxide.
Optionally, the solid electrolyte comprises Li 10 GeP 2 S 12 （LGPS）、Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 （LATP）、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 （LAGP）、Li 7 La 3 Zr 2 O 12 (LLZO).
Optionally, the silicon-based compound comprises at least one of tetraethyl orthosilicate, trishydroxysilylpropylamine, a silicon-based hydroxy-carboxy-silane coupling agent, diphenyldihydroxysilane.
Optionally, the high concentration electrolyte includes a lithium salt and a solvent.
Optionally, the lithium salt comprises at least one of lithium difluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate, and lithium hexafluorophosphate.
Optionally, the solvent comprises a carbonate-based compound.
Optionally, the carbonate based compound comprises at least one of diethyl carbonate DEC, dimethyl carbonate DMC, ethyl methyl carbonate EMC, ethylene carbonate EC, propylene carbonate FEC.
Optionally, the concentration range of the high-concentration electrolyte is: 3-8 mol/L.
Optionally, the concentration of the high-concentration electrolyte is: 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8 mol/L or any value in between any two values.
Optionally, the encapsulation structure is a network cross-linked structure; the solid electrolyte, the silicon-based compound and the high-concentration electrolyte are filled in the reticular cross-linked structure. Wherein the high concentration electrolyte can provide a large amount of free Li + And lithium salt anions are aggregated to form ion clusters, a unique rapid conduction channel is formed through the connection of electrolyte fillers, and a silicon-based additive can react with metallic lithium, so that the stability of the interface of the solid electrolyte membrane and the metallic lithium is further improved. The semisolid electrolyte membrane formed after solidification has high tensile strength and can inhibit the growth of dendrites to a certain extent. The difference from the prior art is that the formed cross-linked network structure not only ensures the ionic conductivity and oxidation resistance of the electrolyte membrane, but also takes the stability of the interface into consideration under the condition of not needing a diaphragm and introducing extra electrolyte.
Optionally, the manner of chemical bonding includes forming at least one of a lithium-containing complex, an alloy of lithium and tin, and Si-O-Li.
The lithium-containing complex can react with a lithium-containing negative electrode simultaneously during polymerization of the packaging structure, and the lithium in the lithium-containing negative electrode is complexed with the polymer; the silicon-based compound can react with metallic lithium to form an organic compound with a Si-O-Li bond, and the tin-containing Lewis acid compound can perform a displacement reaction with the metallic lithium to form an alloy of lithium and tin, so that the interface stability between the solid film and the metallic lithium is further stabilized.
Further, the polyhydroxy glyceryl ether compound contains a large number of hydroxyl groups, and when the polyhydroxy glyceryl ether compound is polymerized, a certain spatial structure can be formed, so that a complex structure is formed with lithium in the lithium-containing negative electrode; meanwhile, the tin-containing Lewis acid participates in the polymerization of the polymerization monomer, and simultaneously can form an alloy of lithium and tin with lithium in the lithium-containing negative electrode, namely, the polyhydroxy glyceryl ether compound and the tin-containing Lewis acid can be mutually crosslinked to form a packaging structure, and can be combined with the lithium-containing negative electrode by chemical bonds to form a Li/Sn compound which plays a role in ionic conductivity; and the coating contains silicon-based compound, which mainly plays a role in connecting the solid film and the electrode, so that the solid film is tightly connected with the lithium-containing cathode, and the problem of the interface between the common solid film and the cathode is remarkably reduced. In addition, the structure formed by curing the polyhydroxy glyceryl ether compound and the tin-containing Lewis acid has high tensile strength, can inhibit dendritic crystal generation and has high oxidation resistance.
The organic conductor and the alloy conductor formed on the interface can not only improve a rapid lithium ion migration channel, but also have a positive effect on buffering larger volume expansion of metal lithium in the charging and discharging processes. Furthermore, the three-dimensional ion-conducting network framework formed in the solid electrolyte membrane has positive significance for improving the stability and conductivity of the whole solid electrolyte membrane. However, in the prior art, a certain problem still exists in the stability of the interface between the solid film and the electrode, and the rapid attenuation of the cycle performance of the battery can be caused by large polarization. This phenomenon can only be alleviated through the introduction of extra electrolyte, and this application does not need extra electrolyte to add, has solidified electrolyte to the membrane inside in this application, need not reintroduce when the equipment electrolyte. In addition, the deposition/exfoliation of the prior art for metallic lithium still has the generation of lithium dendrites, resulting in the occurrence of a short circuit condition of the battery due to the instability of the interfacial properties; the packaging structure is chemically combined with the lithium-containing cathode, so that the connection between the solid film and the cathode can be enhanced to form a whole, and the problem of unstable interface between the solid film and the cathode is greatly reduced.
Optionally, the polymer electrolyte membrane has a thickness of 5 to 30 μm.
Optionally, the polymer electrolyte membrane has a thickness of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, or any number between any two of the values.
If the thickness of the solid film is too thin, the huge volume expansion of the metallic lithium during charging cannot be inhibited, resulting in the rupture of the film itself; if the thickness of the film is too thick, the ion migration distance is large, resulting in increased polarization and capacity fade.
Another aspect of the present application is to provide a method for preparing the polymer electrolyte membrane as described in any one of the above.
Optionally, the preparation method comprises mixing tin-containing lewis acid, a polymeric monomer, a solid electrolyte, a silicon-based compound and a high-concentration electrolyte, coating the mixture on the surface of a lithium-containing negative electrode, and curing in situ to obtain the polymer electrolyte membrane.
Alternatively, a tin-containing lewis acid, a polymeric monomer, a solid electrolyte, a silicon-based compound, and a high-concentration electrolytic solution are mixed and stirred to obtain a mixture.
Optionally, the conditions of agitation include: the temperature is 5-40 ℃; the time is 0.1-6 h. For example, the temperature can be 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or any value between any two values. The time may be 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 2h, 3h, 4h, 5h, 6h, or any number between any two of the values.
Optionally, the preparation method comprises: (1) mixing a tin-containing lewis acid with a polymeric monomer to form a solution I; (2) adding a solid electrolyte and a silicon-based compound into the solution I to obtain a solution II; (3) adding the high-concentration electrolyte into the solution II to obtain a solution III; (4) and coating the solution III on the surface of the lithium-containing negative electrode, and curing in situ to obtain the polymer electrolyte membrane.
Wherein, if all raw materials are directly mixed to prepare the solid film, partial substances may not be fully dissolved, so that the uniformity of the solution is poor; in addition, if the stirring time is too long until the uniform stirring is not carried out before curing, uniformity of the entire solid film may not be ensured; moreover, the problem of premature curing of part of raw materials and the like can be caused by too long stirring time, and the formation of a solid film which is not favorable for subsequent in-situ curing is avoided; through the step-by-step addition, each substance can be ensured to be uniform within a specified time, the time is saved, the uniformity of the whole film can be improved, the original performance of the raw materials can be maintained to a greater extent, and the performance of the solid film is further enhanced.
Optionally, in the solution I, the molar concentration of the tin-containing Lewis acid is 2-10 mmol/L. Wherein if the concentration of the tin-containing lewis acid compound is too high, the cured film may have poor flexibility and lower conductivity, and if the concentration of the tin-containing lewis acid compound is too low, the film may have poor strength and may not prevent the growth of dendrites.
Alternatively, the molar concentration of the tin-containing Lewis acid is 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L or any value between any two values.
Optionally, the mass ratio of the polymerized monomer, the solid electrolyte, the silicon-based compound and the high-concentration electrolyte is (25-89): (1-33): (2-47): (2-57).
If the concentration of the tin-containing lewis acid compound is too high, the cured film may have poor flexibility and lower conductivity, and if the concentration of the tin-containing lewis acid compound is too low, the film may have poor strength and may not prevent the growth of dendrites. The tin-containing Lewis acid compound not only can be crosslinked and polymerized with a polymerization monomer to form a packaging structure, but also can react with metallic lithium to generate an alloy of lithium and tin, namely, tin is simultaneously connected with the packaging structure and the metallic lithium to form the connection between a polymer film and the metallic lithium, thereby reducing the unstable interface between the polymer film and the metallic lithium.
If the content of the silicon-based compound is too low, the silicon-based compound cannot react with a lithium metal cathode well, so that the instability of an interface is caused; if the content is too high, the battery performance may be adversely affected, corresponding to the introduction of new impurities. Further, if the content of the solid electrolyte is low, the conductivity of the solid electrolyte membrane may be low, and if the content of the solid electrolyte is too high, the flexibility of the entire membrane may be drastically reduced, brittleness may be increased, and there may be a possibility of brittleness under a large stress.
Optionally, the conditions of in situ curing: the temperature is 25-45 ℃; the time is 5-8 h.
Optionally, the temperature is 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃ or any value between any two values; the time period is 5h, 6h, 7h, 8h or any value in between any two values.
Preferably, the polymeric monomer comprises a polyhydroxy glyceryl ether compound. After being polymerized with tin-containing Lewis acid, the modified polyurethane has higher Young modulus.
The invention uses the solvent containing tin Lewis acid compound and cross-linking with tin Lewis acid compound to polymerize and form solid film, which improves the tensile strength of the whole film and inhibits the generation of dendritic crystal; filling a solid electrolyte material in the solid film to improve the conductivity of the solid film; and further introducing a high-concentration electrolyte to be effectively encapsulated in the solid electrolyte membrane, so as to further improve the electrochemical performance of the solid electrolyte membrane; in addition, in order to improve the interface stability of the solid electrolyte membrane and the metal lithium cathode, a silicon-based compound is introduced, and the silicon-based compound further reacts with the metal lithium cathode, so that the whole solid electrolyte membrane is connected with the metal lithium through a hydrogen bond, and the interface stability of the solid electrolyte membrane is well ensured.
In addition, the polymer crosslinked by the polyhydroxy glycerol ether and the tin-containing Lewis acid has a plurality of oxygen-containing structures and lone-pair electrons, and can be complexed with lithium, so that the interface condition of the solid polymer electrolyte membrane and the metal lithium is further improved.
Further, Lewis acid and polyhydroxy glycerol ether are subjected to polymerization reaction, and the solid electrolyte, the silicon-based compound and the high-concentration electrolyte are encapsulated in the solid electrolyte, so that the ionic conductivity and the oxidation resistance of the electrolyte membrane are improved through the synergistic effect of the components. At the same time, the high concentration electrolyte can provide a large amount of free Li + And lithium salt anions are aggregated to form ion clusters, a unique rapid conduction channel is formed through the connection of electrolyte fillers, and a silicon-based additive can react with metallic lithium, so that the stability of the interface of the solid electrolyte membrane and the metallic lithium is further improved.
Alternatively, the preparation process is carried out in an inert gas.
Optionally, the inert gas comprises at least one of helium, neon, argon, krypton, and xenon.
Preferably, the preparation method comprises: (1) dissolving a Lewis acid compound in a polyhydroxy glyceryl ether solution, stirring for 5-20 min, and preparing into a solution of 2-10 mmol/l; (2) 0.05-0.5 g of solid electrolyte material and 0.1-1 g of silicon-based compound are weighed and added into the solution (1-2 g), and stirring is carried out for 1-6 h; (3) adding prepared high-concentration electrolyte (0.5-1.5 g) into the mixed solution, and continuously stirring for 0.5-2 h; (4) and (4) sucking 50-200 ul of the mixed liquid in the step (3) and coating the mixed liquid on a metal lithium foil until the mixed liquid is solidified, wherein the solidification time is 5-8 h, and a solid electrolyte membrane with the thickness of 5-30 microns is obtained.
Alternatively, the stirring time of step (1) may be 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min or any value in between any two values.
Alternatively, the stirring time of step (2) may be 1h, 2h, 3h, 4h, 5h, 6h, or any value in between any two values.
Alternatively, the stirring time of step (3) may be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, or any number between any two of the values.
Another aspect of the present invention is to provide a battery.
Optionally, the cell comprises a positive electrode, a negative electrode and a polymer electrolyte membrane as described in any of the above.
Alternatively, the lithium metal foil with the solid electrolyte membrane was cut into circular disks with a diameter of 16mm, NCM811 was selected, and the areal density was 15mg/cm 2 Cutting into 13mm diameter wafer; the batteries were assembled in a glove box. Wherein the process does not require the introduction of a separator and an additional electrolyte.
Alternatively, in the lithium metal secondary battery of the present invention, the positive electrode includes lithium cobaltate, lithium manganate, LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiNi 0.6 Co 0.2 Mn 0.2 O 2 And the like. The negative electrode includes lithium metal, lithium aluminum alloy, lithium magnesium alloy, lithium boron alloy, or the like.
In contrast to the prior art, the present application has the following advantages (the advantages of the substances and methods are described separately):
(1) the polymer electrolyte membrane comprises an encapsulation structure, wherein the encapsulation structure is formed by polymerizing tin-containing Lewis acid and a polymerization monomer, so that the tensile strength of the whole membrane is improved, and the encapsulation structure can be combined with a negative electrode by a chemical bond to form a whole body so as to inhibit the generation of dendritic crystals; a solid electrolyte material is filled in the packaging structure, so that the conductivity of the solid film is improved; the high concentration electrolyte can provide a large amount of free Li + And lithium salt anions are aggregated to form ion clusters, so that the electrochemical performance of the solid electrolyte membrane is improved; introducing a silicon-based compound to further react with the metallic lithium cathode, so that the whole solid electrolyte membrane is connected with the metallic lithium through a chemical bond, and the interface stability of the solid electrolyte membrane and the metallic lithium cathode is improved; the ionic conductivity and the oxidation resistance of the electrolyte membrane are improved through the synergistic effect among the components, a unique rapid conduction channel is formed through the connection of the electrolyte filler, and the silicon-based additive can react with the lithium metal, so that the stability of the interface of the solid electrolyte membrane and the lithium metal is further improved.
(2) According to the method, the raw materials are added step by step, so that the substances can be mixed more uniformly, and adverse reactions such as precipitation before solidification are reduced; furthermore, the mixed solution is coated on the surface of the lithium metal and then subjected to in-situ polymerization, so that the compatibility with the negative electrode can be increased, the reaction with the lithium metal can be generated while the lithium metal is solidified, the solid electrolyte membrane and the lithium metal negative electrode are further tightly combined together to form a whole, and the interface stability between the solid electrolyte membrane and the lithium metal negative electrode is greatly improved.
Drawings
FIG. 1 is an SEM (scanning Electron microscope) image of a lithium metal negative electrode after 20 weeks of cycling provided in example 1 of the present application;
FIG. 2 is an SEM (scanning Electron microscope) image of a lithium metal negative electrode after 20 weeks of cycling provided in comparative example 1 of the present application;
FIG. 3 is an SEM (scanning Electron microscope) image of a lithium metal negative electrode after 20 weeks of cycling provided by comparative example 2 of the present application;
FIG. 4 is an SEM (scanning Electron microscope) image of a lithium metal negative electrode after 20 weeks of cycling provided in comparative example 3 of the present application;
FIG. 5 is a linear cyclic voltammogram of a solid electrolyte membrane of example 1 of the present application and comparative examples 1, 2, and 3; wherein, the abscissa is voltage, the unit is V, the ordinate is current, the unit is A;
FIG. 6 is a voltage-specific capacity curve diagram of the batteries prepared in examples 1 to 4 and comparative examples 1 to 5 of the present application, which shows the data trend of the battery voltage and specific capacity; wherein the abscissa is specific capacity, the unit is mAh/g, and the ordinate is voltage, the unit is V; FIG. 6 (a) shows the results of examples 1 to 4; FIG. 6 (b) shows the results of comparative examples 1 to 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below. It is to be understood that the description herein is only illustrative of the present application and is not intended to limit the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and the terms used herein in the specification of the present application are for the purpose of describing particular embodiments only and are not intended to limit the present application. The reagents and instruments used in the present invention are commercially available, and the characterization means involved can be referred to the description in the prior art, which is not repeated herein.
For a further understanding of the present application, reference is made to the following detailed description of the preferred embodiments.
Example 1
Under argon atmosphere, the following operations were carried out:
(1) taking Sn (OTF) 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min,preparing the solution into 2mmol/l solution, and taking 1g of the solution; (2) 0.05 g of LGPS solid electrolyte material and 1g of tetraethyl orthosilicate are weighed and added into the solution, and the solution is stirred for 2 hours; (3) the mixed solution was added with a prepared high concentration electrolyte (0.1 g) 3M LiTFSI (C) 2 F 6 LiNO 4 S 2 Lithium bistrifluoromethanesulfonylimide), wherein the solvent of the high-concentration electrolyte is DEC, and the solution is continuously stirred for 2 hours; (4) and (3) sucking 50ul of the mixed solution in the step (3) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 5 hours, and a solid electrolyte membrane with the thickness of 5 microns is obtained.
Example 2
Under argon atmosphere, the following operations were carried out:
(1) taking SnCl 4 Dissolving in trihydroxymethyl ethane triglycidyl ether solvent, stirring for 5min, preparing into 5mmol/l solution, and collecting 1.2 g; (2) 0.5g of LATP solid electrolyte material and 0.1g of trihydroxysilyl propylamine are weighed into the solution and stirred for 2 hours; (3) adding prepared high-concentration electrolyte (0.5 g) 5M LiFSI (F) into the mixed solution 2 NO 4 S 2 Li, lithium bis (fluorosulfonyl) imide), wherein the solvent of the high-concentration electrolyte is EC, and the solution is continuously stirred for 1 h; (4) and (4) sucking 150 ul of the mixed solution in the step (3) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 8 hours, and the solid electrolyte membrane with the thickness of 10 microns is obtained.
Example 3
Under argon atmosphere, the following operations were carried out:
(1) taking SnCl 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 1.5 g; (2) 0.25 g of LAGP solid electrolyte material and 0.5g of silicon-based hydroxyl-carboxyl-silane coupling agent are weighed and added into the solution, and stirred for 2 hours; (3) the prepared high-concentration electrolyte (1 g) 6M LiDFOB (C) was added to the above-mentioned mixed solution 2 BF 2 LiO 4 Lithium difluoro (oxalato) borate), wherein the solvent of the high-concentration electrolyte is EMC, and the solution is continuously stirred for 1.5 h; (4) absorbing 200ul of the mixed liquid in the step (3) and coating the mixed liquid on the metal lithium foilUntil cured, the curing time was 5h, resulting in a solid electrolyte membrane 8 microns thick.
Example 4
Under argon atmosphere, the following operations were carried out:
(1) taking Sn (OTF) 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 1.8 g; (2) 0.35 g of LLZO solid electrolyte material and 0.6 g of diphenyldihydroxy silane are weighed and added into the solution, and stirred for 2 hours; (3) adding prepared high-concentration electrolyte (1.5 g) 3M LiPF6 (lithium hexafluorophosphate) into the mixed solution, wherein the solvent of the high-concentration electrolyte is DMC, and continuously stirring for 2 h; (4) and (4) sucking 150 ul of the mixed solution in the step (3) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 5 hours, and a solid electrolyte membrane with the thickness of 6 microns is obtained.
Comparative example 1
Under argon atmosphere, the following operations were carried out:
0.5g of LGPS solid electrolyte material and 0.5g of tetraethyl orthosilicate are weighed and added into a prepared high-concentration electrolyte 3M LiTFSI (C) 2 F 6 LiNO 4 S 2 Lithium bistrifluoromethanesulfonylimide), wherein the solvent of the high concentration electrolyte is DEC, continuously stirred for 2h, used when assembling the battery, this process requires a separator.
Comparative example 2
Under argon atmosphere, the following operations were carried out:
taking Sn (OTF) 2 Dissolving in diethyl carbonate (DEC) solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 2 g; (2) 0.5g of LGPS solid electrolyte material and 1g of tetraethyl orthosilicate are weighed and added into the solution, and stirred for 2 hours; (3) adding the prepared high-concentration electrolyte 4M LiTFSI (C) into the mixed solution 2 F 6 LiNO 4 S 2 Lithium bistrifluoromethanesulfonylimide), wherein the solvent of the high-concentration electrolyte is DEC, and the uniform electrolyte is obtained by continuously stirring for 2 hours and is used when a battery is assembled, and a diaphragm is required in the process.
Comparative example 3
Under argon atmosphere, the following operations were carried out:
(1) taking Sn (OTF) 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 1.5 g; (2) weighing 1g of tetraethyl orthosilicate, adding the tetraethyl orthosilicate into the solution, and stirring for 2 hours; (3) adding prepared high-concentration electrolyte 5M LiTFSI (C) into the mixed solution 2 F 6 LiNO 4 S 2 Lithium bis (trifluoromethanesulfonyl) imide), wherein the solvent of the high-concentration electrolyte is DMC, and the solution is continuously stirred for 2 hours; (4) and (3) sucking 50ul of the mixed solution in the step (3) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 5 hours, and a solid electrolyte membrane with the thickness of 5 microns is obtained.
Comparative example 4
Under argon atmosphere, the following operations were carried out:
(1) taking Sn (OTF) 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 1 g; (2) 0.5g of LGPS solid electrolyte material is weighed and added into the solution, and the solution is stirred for 2 hours; (3) adding the prepared high-concentration electrolyte 3M LiTFSI (C) into the mixed solution 2 F 6 LiNO 4 S 2 Lithium bis (trifluoromethanesulfonylimide), wherein the solvent of the high-concentration electrolyte is EC, and continuously stirring for 2 h; (4) and (3) sucking 50ul of the mixed solution in the step (3) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 5 hours, and a solid electrolyte membrane with the thickness of 5 microns is obtained.
Comparative example 5
Under argon atmosphere, the following operations were carried out:
(1) taking Sn (OTF) 2 Dissolving in trimethylolpropane triglycidyl ether solvent, stirring for 5min, preparing into 2mmol/l solution, and collecting 1.2 g; (2) 0.5g of LGPS solid electrolyte material and 0.5g of tetraethyl orthosilicate are weighed and added into the solution, and stirred for 2 hours; (3) and (3) sucking 50ul of the mixed solution in the step (2) and coating the mixed solution on a metal lithium foil until the mixed solution is solidified, wherein the solidification time is 5 hours, and a solid electrolyte membrane with the thickness of 5 microns is obtained.
Performance test
Cutting the metal lithium foil with the solid electrolyte membrane into round pieces with the diameter of 16mm, selecting lithium cobaltate as a positive electrode and the surface density of 15mg/cm 2 Cutting into 13mm diameter wafer; and assembling into a battery.
1. Energy density of battery
The energy density was tested by assembling a pouch cell of 4Ah using the protocols of examples 1-4 and comparative examples 1-5. According to the test steps, under the environment of room temperature (25 ℃ and 2 ℃), the test is carried out according to the following steps that 1) the discharge is carried out to 3V according to the current of 0.2C, and the standing is not less than 30 min; 2) charging to 4.3V (charging time is not more than 8h) according to a charging mode of 0.2C, and standing for not less than 30 min; 3) repeating the step 1), and measuring the discharge energy E (calculated by Wh); 4) repeating the step 2) -3) for 2 times, and taking the average value Eaverage of the discharge energy E for 3 times; 5) measuring the mass M (in kg) of the test object with a balance; 6) the discharge energy density PED (in Wh/kg) of the test object is calculated by the following formula: PED = eaves/M.
The batteries were assembled in a glove box. In which a stainless steel/solid film/stainless steel cell was assembled, the ac impedance at normal and high temperature of the different components was tested on an electrochemical workstation and the conductivity was calculated as shown in table 1.
TABLE 1 basic Performance and energy Density results of solid electrolyte membranes of examples and comparative examples assembled into a cell
As shown in Table 1, the cycle performance test was performed by a LAND cell test system with a constant current charge and discharge voltage range of 3-4.3V. After the lithium battery prepared in example 1 is cycled for 20 cycles, the specific capacity is maintained at 192mAh/g, the capacity retention rate reaches 97%, and the energy density reaches 403 wh/kg; after the lithium battery prepared in the embodiment 2 is cycled for 20 circles, the specific capacity is maintained at 188mAh/g, the capacity retention rate reaches 96%, and the energy density reaches 396 wh/kg; after the lithium battery prepared in the embodiment 3 is cycled for 20 circles, the specific capacity is maintained at 187mAh/g, the capacity retention rate reaches 95%, and the energy density reaches 395 wh/kg; the lithium battery prepared in the embodiment 4 has high cycle stability, after 20 cycles, the capacity retention rate reaches 94%, and the energy density reaches 389wh/kg, which shows that the cured electrolyte membrane has high electrochemical performance in a multi-component strategy. As can be seen from the graph (b) in fig. 6, comparative example 1, which did not undergo polymerization without introduction of tin-containing lewis acid compound, exhibited lower ionic conductivity, exhibited only 144mAh/g capacity exertion at 20 cycles, exhibited faster capacity fading in subsequent cycles, lower ionic conductivity, higher impedance, severe polarization, and resulted in extremely low capacity exertion. In comparative example 2, polymerization was also not allowed to occur, and when the cycle was 20 cycles, the capacity exhibited was only 157mAh/g, and the capacity retention rate reached 81%. In addition, at higher voltages (> 4V), electrolyte systems that do not polymerize are susceptible to oxidation, solvent molecules are oxidized, resulting in large active lithium loss, leading to lower capacity and drastic decay, failing to maintain stable cycling performance. Comparative examples 3 to 4 failed to establish strong interfacial stability with the electrode due to the absence of a solid electrolyte or a silicon-containing compound and the lower conductivity greatly resulted in capacity fade. Wherein the tin-containing lewis acid compound was less in the entire solid film and the formed Li/Sn compound was also less, mainly functioning as ion conductivity, so that the comparative example which did not contain the tin-containing lewis acid compound was relatively poor in conductivity; the comparative example containing no silicon-based compound had poor interface stability because the silicon-based compound contained a relatively large amount of silicon-based compound and mainly served to connect the solid film and the electrode. Comparative example 5 also showed low ionic conductivity due to lack of high concentration of electrolyte, and the formed SEI film was relatively unstable, so that the capacity retention rate was only 86% after 20 cycles. Wherein the Young's modulus reflects the tensile strength of the solid film, and examples 1-4 all show higher tensile strength, which can buffer the huge volume expansion and dendrite generation generated by the lithium metal when charged; in addition, the tensile strength of example 2 was more than 2 times that of comparative example 4, and excellent mechanical properties were exhibited.
2. Oxidation resistance of solid electrolyte membrane
Assembling a Li/solid-state membrane/stainless steel battery, and testing linear cyclic voltammetry curves of different components on an electrochemical workstation, wherein the test voltage ranges are as follows: -0.5-8V. As can be seen from fig. 5, at around 4V, the solid-state membranes of comparative examples 1 to 3 began to oxidize, indicating that the solid-state membranes were poor in oxidation resistance and underwent decomposition reaction at high voltage. The solid film of example 1 was observed to be oxidized at a voltage of about 6V after curing and the synergistic effect of the multiple components, indicating that the solid film has a wider voltage window and strong oxidation resistance.
3. Stability of the interface
In order to observe the interfacial stability between the solid film and the negative electrode, the lithium metal negative electrodes of example 1 and comparative examples 1 to 3 were observed after the above cycle for 20 weeks, and the results are shown in fig. 1 to 4.
Fig. 1 is an SEM surface topography of the surface of lithium metal after 20 cycles of the example 1, as shown in fig. 1, it can be seen that the surface of lithium metal is deposited as large oval particles, no dendrite is observed, the lithium metal is deposited uniformly, and the interface performance is better. FIG. 2 is an SEM surface topography of the surface of lithium metal after 20 cycles of comparative example 1, and it can be seen that the surface of lithium metal has many tiny dendrites, and the deposition of the surface of lithium metal is not uniform and the interface performance is poor. Fig. 3 is an SEM surface topography of the surface of metallic lithium after 20 cycles of comparative example 2, and it can be found that there are many tiny cracks on the surface of metallic lithium due to the fact that the SEI film is broken by large volume expansion during charging, and thus the SEI film is continuously consumed and reformed, which causes unstable interfacial properties, and thus shows capacity fade. Fig. 4 is an SEM surface topography of the surface of the lithium metal after 20 cycles of the comparative example 3, and it can be found that the surface of the lithium metal has many micro-porous structures, which may not well block the contact between the electrolyte and the lithium metal, and continuously consume the electrolyte, and the poor interface property may cause serious polarization and capacity fading.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A polymer electrolyte membrane is characterized by comprising a packaging structure connected with a lithium-containing negative electrode in a chemical bond mode, and a solid electrolyte, a silicon-based compound and a high-concentration electrolyte filled in the packaging structure;
the packaging structure is obtained by crosslinking tin-containing Lewis acid and a polymerization monomer;
the polymerized monomer comprises a polyhydroxy glyceryl ether compound;
the electrolyte comprises at least one of sulfide ceramic, polyphosphate type ceramic and garnet lithium lanthanum zirconium oxide;
the silicon-containing compound comprises at least one of tetraethyl orthosilicate, trihydroxysilyl propylamine and diphenyl dihydroxysilane;
the high-concentration electrolyte comprises a lithium salt and a solvent;
the concentration range of the high-concentration electrolyte is as follows: 3-8 mol/L.
2. The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte membrane comprises: 25-89 parts by mass of a packaging structure; 1-33 parts of solid electrolyte; 2-47 parts of a silicon-based compound; 2-57 parts of high-concentration electrolyte.
3. The polymer electrolyte membrane according to claim 1, wherein the mass ratio of the tin-containing lewis acid to the polymerized monomer is: (0.001-0.1) and (25-89).
4. The polymer electrolyte membrane according to claim 1,
the polyhydroxy glycerol ether compound comprises at least one of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether;
the tin-containing Lewis acid comprises SnCl 4 、SnCl 2 、Sn(OTF) 2 At least one of;
the lithium salt comprises at least one of lithium difluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium hexafluorophosphate;
the solvent comprises at least one of cyclic DEC diethyl carbonate, DMC dimethyl carbonate, EMC ethyl methyl carbonate, EC ethylene carbonate and FEC propylene carbonate.
5. The polymer electrolyte membrane according to claim 1, wherein the encapsulating structure is a network cross-linked structure; the solid electrolyte, the silicon-based compound and the high-concentration electrolyte are filled in the reticular cross-linked structure.
6. The polymer electrolyte membrane according to claim 1, wherein the means of chemical bonding comprises at least one of forming a lithium-containing complex, an alloy of lithium and tin, and Si-O-Li.
7. The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte membrane has a thickness of 5 to 30 μm.
8. A method for producing a polymer electrolyte membrane according to any one of claims 1 to 7, comprising:
(1) mixing a tin-containing lewis acid with a polymeric monomer to form a solution I;
(2) adding a solid electrolyte and a silicon-based compound into the solution I to obtain a solution II;
(3) adding the high-concentration electrolyte into the solution II to obtain a solution III;
(4) and coating the solution III on the surface of the lithium-containing negative electrode, and curing in situ to obtain the polymer electrolyte membrane.
9. The preparation method according to claim 8, wherein in the solution I, the molar concentration of the tin-containing Lewis acid is 2 to 10 mmol/L;
conditions for in situ curing: the temperature is 25-45 ℃; the time is 5-8 h.
10. A battery comprising a positive electrode, a negative electrode and the polymer electrolyte membrane according to any one of claims 1 to 7.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033130A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | High polymer solid electrolyte and secondary battery |
| CN103904361A (en) * | 2012-12-28 | 2014-07-02 | 财团法人工业技术研究院 | Polymerized colloidal electrolyte and polymer lithium secondary battery |
| CN108933290A (en) * | 2017-08-09 | 2018-12-04 | 浙江林奈新能源有限公司 | A kind of film for lithium ion battery solid electrolyte |
| CN109888380A (en) * | 2019-03-07 | 2019-06-14 | 苏州大学 | A kind of solid polymer electrolyte and its application in lithium metal battery |
| CN111162314A (en) * | 2019-12-25 | 2020-05-15 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN111653822A (en) * | 2020-06-09 | 2020-09-11 | 北京化工大学 | Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof |
| CN112701348A (en) * | 2020-12-28 | 2021-04-23 | 南方科技大学 | Polymer solid electrolyte, all-solid-state lithium battery and preparation method thereof |
| CN113571768A (en) * | 2021-09-23 | 2021-10-29 | 浙江金羽新能源科技有限公司 | Modified aluminum-based polymer and preparation method thereof, high-pressure-resistant solid polymer electrolyte membrane and preparation method thereof, and lithium metal secondary battery |
| CN114292484A (en) * | 2021-12-02 | 2022-04-08 | 厦门大学 | Interpenetrating network structure layer, in-situ preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9601804B2 (en) * | 2008-11-10 | 2017-03-21 | Samsung Electronics Co., Ltd. | Gel polymer electrolyte, lithium battery including gel polymer electrolyte, and method of preparing gel polymer electrolyte |
| KR20120078235A (en) * | 2010-12-31 | 2012-07-10 | 충북대학교 산학협력단 | Lewis acid complex-based polymer electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| TWI476976B (en) * | 2012-12-28 | 2015-03-11 | Ind Tech Res Inst | Polymerized gel electrolyte and polymer lithium battery |
-
2022
- 2022-04-24 CN CN202210451854.6A patent/CN114583258B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033130A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | High polymer solid electrolyte and secondary battery |
| CN103904361A (en) * | 2012-12-28 | 2014-07-02 | 财团法人工业技术研究院 | Polymerized colloidal electrolyte and polymer lithium secondary battery |
| CN108933290A (en) * | 2017-08-09 | 2018-12-04 | 浙江林奈新能源有限公司 | A kind of film for lithium ion battery solid electrolyte |
| CN109888380A (en) * | 2019-03-07 | 2019-06-14 | 苏州大学 | A kind of solid polymer electrolyte and its application in lithium metal battery |
| CN111162314A (en) * | 2019-12-25 | 2020-05-15 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN111653822A (en) * | 2020-06-09 | 2020-09-11 | 北京化工大学 | Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof |
| CN112701348A (en) * | 2020-12-28 | 2021-04-23 | 南方科技大学 | Polymer solid electrolyte, all-solid-state lithium battery and preparation method thereof |
| CN113571768A (en) * | 2021-09-23 | 2021-10-29 | 浙江金羽新能源科技有限公司 | Modified aluminum-based polymer and preparation method thereof, high-pressure-resistant solid polymer electrolyte membrane and preparation method thereof, and lithium metal secondary battery |
| CN114292484A (en) * | 2021-12-02 | 2022-04-08 | 厦门大学 | Interpenetrating network structure layer, in-situ preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "Solid polymer electrolyte based on ionic bond or covalent bond functionalized silica nanoparticles";Ji Hu,et al.;《RSC Advances》;20171204;第7卷;全文 * |
| "Strong Lewis Acid−Base and Weak Hydrogen Bond Synergistically Enhancing Ionic Conductivity of Poly(ethylene oxide)@SiO2 Electrolytes for a High Rate Capability Li-Metal Battery";Zhong Xu,et al.;《ACS Applied Materials & Interfaces》;20200212;第12卷;全文 * |
| 交联封装实现高效的水稳定锂金属负极（英文）;肖也等;《Science Bulletin》;20200511(第11期);全文 * |
| 含PVDF-HFP多孔骨架和交联PEG的锂离子凝胶膜制备与性能;崔振宇等;《功能材料》;20070220(第02期);全文 * |
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