CN113299984A - Single-ion conductor polymer solid electrolyte membrane and preparation method and application thereof - Google Patents
Single-ion conductor polymer solid electrolyte membrane and preparation method and application thereof Download PDFInfo
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a single-ion conductor polymer solid electrolyte membrane and a preparation method and application thereof. The single ion conductor polymer solid electrolyte membrane includes: 5-50 parts by weight of lithium-containing monomer, 5-25 parts by weight of crosslinking monomer, 1-30 parts by weight of polymer, 0-20 parts by weight of plasticizer, 0-15 parts by weight of inorganic particles and lithium salt; wherein the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is 1: (1-16). The single-ion conductor polymer solid electrolyte membrane has higher ionic conductivity and lithium ion migration number, is simple in preparation process, and can be used for a solid lithium battery to reduce concentration polarization, improve discharge specific capacity and prolong cycle life.
Description
Technical Field
The invention belongs to the field of electrochemical devices, and particularly relates to a single-ion conductor polymer solid electrolyte membrane and a preparation method and application thereof.
Background
At present, lithium ion batteries become the most important energy storage devices, the traditional lithium batteries use organic electrolyte, the chemical properties of the traditional lithium batteries are unstable, the traditional lithium batteries are highly flammable and have strong corrosivity, potential safety hazards exist, solid-state lithium batteries become one of the technical directions of future batteries, and the solid-state electrolyte is the most critical material. The solid electrolyte includes oxides, sulfides, polymers, etc., wherein the solid polymer electrolyte has the advantages of inhibiting the growth of lithium dendrites, reducing the reactivity between the electrolyte and electrodes, being safe and reliable, being easy to process, etc., and is considered as a novel electrolyte material which solves the defects of the current liquid electrolyte, improves the performance of the lithium ion battery, and firstly forms the commercialization of the solid polymer lithium battery. However, how to combine a higher lithium ion transport number and lithium ion conductivity of the solid electrolyte membrane still needs to be further improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
The present invention has been completed based on the following findings of the inventors:
the existing double-ion solid polymer electrolyte mainly comprises a polymer matrix such as PEO, PMMA, PVDF, PAN and the like and various lithium salts, wherein the lithium salts are dissociated in the polymer to form lithium ions and anions, and the anions and the lithium ions can respectively migrate to an anode and a cathode in the charging and discharging processes of the battery, so that concentration gradient occurs in the electrolyte due to the large charge density, the slow migration rate and the fast migration rate of the anions, a polarization potential opposite to an external electric field is generated, the ion migration is blocked, the energy density of the battery is reduced, the service life of the battery is prolonged, the migration number of the lithium ions of most polymer electrolytes is less than 0.2, and the application of the electrolyte is greatly limited. The single ion transmission type polymer electrolyte is prepared by fixing anions on a polymer main chain by covalent bonds, only cations are transferred, the reaction of the anions and electrodes can be reduced, concentration polarization is reduced, high lithium ion conductivity of the traditional polymer solid electrolyte is ensured, and simultaneously, the high lithium ion transfer number is also achieved, so that the effects of improving the transmission efficiency of lithium ions and promoting the lithium ion conduction are achieved.
Therefore, an object of the present invention is to provide a single-ion conductor polymer solid electrolyte membrane having high ionic conductivity and lithium ion transport number, and simple preparation process, which can be used in a solid lithium battery, reduce concentration polarization, increase specific discharge capacity and prolong cycle life.
In one aspect of the invention, a single ion conductor polymer solid electrolyte membrane is presented. According to an embodiment of the present invention, the polymer solid electrolyte membrane includes: 5-50 parts by weight of lithium-containing monomer, 5-25 parts by weight of crosslinking monomer, 1-30 parts by weight of polymer, 0-20 parts by weight of plasticizer, 0-15 parts by weight of inorganic particles and lithium salt; wherein the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is 1: (1-16). The inventor finds that the single-ion conductor polymer solid electrolyte membrane with the components and the proportion has higher ionic conductivity and lithium ion migration number, has simple preparation process, can be used for a solid lithium battery to reduce concentration polarization, improve discharge specific capacity and prolong cycle life, and particularly has the lithium ion conductivity of not less than 1 multiplied by 10-5S/cm, and the transference number of lithium ions is not less than 0.5.
According to an embodiment of the present invention, the chemical repeating units of the single ion conductor polymer solid state electrolyte membrane are as
According to the embodiment of the invention, the lithium-containing monomer has the structural formula
Wherein x is an integer of 2 to 40, and R is a hydrogen atom or a methyl group.
According to an embodiment of the present invention, the crosslinking monomer includes at least two epoxy groups, the epoxy groups being at least one selected from ethoxy, propoxy and butoxy groups.
According to an embodiment of the present invention, the crosslinking monomer is at least one selected from trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
According to an embodiment of the present invention, the polymer is at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polycarbonate.
According to an embodiment of the invention, the inorganic particles are selected from Al2O3、SiO2Molecular sieves, Li1.5Al0.5Ge1.5P3O12And Li1.4Al0.4Ti1.6(PO4)3At least one of (a).
According to an embodiment of the present invention, the inorganic particles have an average particle diameter of 5 to 600 nm.
According to an embodiment of the present invention, the plasticizer is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, tetraglyme, and succinonitrile.
According to an embodiment of the present invention, the thickness of the single ion conductor polymer solid electrolyte membrane is 10 to 500 μm.
According to an embodiment of the present invention, the lithium ion conductivity of the single ion conductor polymer solid electrolyte membrane is not less than 1 × 10-5S/cm, and the transference number of lithium ions is not less than 0.5.
In another aspect of the present invention, the present invention provides a method for preparing the above single-ion conductor polymer solid electrolyte membrane. According to an embodiment of the invention, the method comprises: (1) mixing lithium-containing monomers, crosslinking monomers, polymers, plasticizers, inorganic particles, lithium salts and organic solvents according to a preset ratio to obtain mixed slurry; (2) and coating the mixed slurry into a film, and heating, polymerizing and curing to obtain the single-ion conductor polymer solid electrolyte membrane. The inventor finds that compared with the prior art, the method is simple and efficient, can be used for large-scale production in a coating mode, and the prepared composite solid polymer electrolyte membrane has higher ionic conductivity and lithium ion migration number, and can be widely applied to solid lithium batteries to reduce concentration polarization, improve discharge specific capacity and prolong cycle life.
According to the embodiment of the invention, the solid content of the mixed slurry is 10-50 wt%.
According to an embodiment of the present invention, the solvent is at least one selected from the group consisting of acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, and acetone.
In yet another aspect of the invention, a solid state lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes a positive electrode, a negative electrode, and the single ion conductor polymer solid electrolyte membrane described above or the single ion conductor polymer solid electrolyte membrane obtained by the method for producing a single ion conductor polymer solid electrolyte membrane described above. Compared with the prior art, the solid-state lithium battery has the advantages that the discharge specific capacity and the charge-discharge efficiency are improved, the stability and the electrochemical cycle performance are higher, the service life is longer, and the commercial prospect is good.
According to an embodiment of the present invention, the active material of the positive electrode includes at least one selected from lithium iron phosphate, lithium cobaltate, and lithium nickel cobalt manganese oxide, and the negative electrode is a lithium metal.
The invention has the following beneficial technical effects:
(1) the single-ion conductor polymer solid electrolyte membrane with the components and the proportion has higher ionic conductivity and lithium ion transference number, and can be used for a solid lithium battery to reduce concentration polarization, improve discharge specific capacity and prolong the cycle life.
(2) The amido in the raw material components can react with sulfonic acid to generate sulfamide, part of amido is changed from primary amine to secondary amine by controlling the reaction condition, the residual active hydrogen on the amido can continuously react with a crosslinking monomer containing epoxy terminal groups, and the polymer with certain mechanical strength is obtained by curing.
(3) The main chain of the monomer with amino and epoxy end groups contains one or more of ethoxy, propoxy and butoxy, and can be complexed and dissociated with lithium ions to conduct the lithium ions.
(4) The metal ions connected with the sulfonic acid groups can be replaced by lithium ions through the processes of water washing, replacement and the like, and finally a part of lithium sulfonate is grafted on a polymer chain.
(5) The method for preparing the single-ion conductor polymer solid electrolyte membrane is simple and efficient, and can be used for large-scale production in a coating mode.
(6) When the solid lithium battery with the single-ion conductor polymer solid electrolyte membrane is used, the concentration polarization is reduced, the discharge specific capacity and the charge-discharge efficiency are improved, the solid lithium battery has high stability and electrochemical cycle performance, the service life can be prolonged, and the commercial prospect is good.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is an SEM image of a single ion conductor polymer solid state electrolyte membrane prepared according to example 1 of the present invention;
FIG. 2 is a graph showing the change of ion conductivity with temperature of a single ion conductor polymer solid electrolyte membrane according to example 1 of the present invention;
FIG. 3 is a graph showing AC impedance to lithium interface reaction before and after polarization and chronoamperometry at 70 ℃ of a single ion conductor polymer solid electrolyte membrane prepared in example 1 according to the present invention.
Fig. 4 is a comparison graph of the charge-discharge specific capacity and charge-discharge efficiency curves of the button cell assembled by the solid electrolyte membrane prepared according to the embodiment 1 and the comparative example 1, the lithium iron phosphate anode and the lithium metal cathode.
Detailed Description
The following describes embodiments of the present invention in detail. The following described embodiments are exemplary and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the present inventionIn one aspect, the present invention provides a single ion conductor polymer solid electrolyte membrane. According to an embodiment of the present invention, the polymer solid electrolyte membrane includes: 5-50 parts by weight of lithium-containing monomer, 5-25 parts by weight of crosslinking monomer, 1-30 parts by weight of polymer, 0-20 parts by weight of plasticizer, 0-15 parts by weight of inorganic particles and lithium salt; wherein the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is 1: (1-16). The inventor finds that the single-ion conductor polymer solid electrolyte membrane with the components and the proportion has higher ionic conductivity and lithium ion migration number, has simple preparation process, can be used for a solid lithium battery to reduce concentration polarization, improve discharge specific capacity and prolong cycle life, and particularly has the lithium ion conductivity of not less than 1 multiplied by 10-5S/cm, and the transference number of lithium ions is not less than 0.5.
The single ion conductor polymer solid electrolyte membrane according to the above embodiment of the present invention will be described in detail.
According to the embodiment of the invention, the lithium-containing monomer and the crosslinking monomer are used as main film forming materials of the polymer solid electrolyte film and provide a conducting group of lithium ions, so that the anions are fixed on the main chain of the polymer by covalent bonds, the lithium ions and the main chain of the polymer are complexed and dissociated in the charge-discharge process, the conduction of the lithium ions is realized, meanwhile, the movement of the anions is inhibited in the charge-discharge process due to the fixing action, the transference number of the lithium ions of the electrolyte film is improved, and the concentration polarization of the solid-state battery is reduced, wherein the polymer is used for improving the film forming property and the mechanical property of the electrolyte film, so that the electrolyte film has better flexibility and plasticity; in addition, the lithium ion complex dissociation group in the invention refers to a group capable of conducting lithium ions, including an ether oxygen group, an ester group and the like, mainly existing in a lithium-containing monomer and a crosslinking monomer, and also existing in a polymer, and the inventor finds that if the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is too small, the lithium ion concentration is too low, and the improvement of the ion conductivity is not facilitated; if the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is too large, the dissociation difficulty of the lithium ions and the complex dissociation groups can be obviously increased,the method is also not beneficial to improving the transference number and the ionic conductivity of the lithium ions, and the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is controlled to be 1: (1 to 16), for example, 1/1, 1/2, 1/3, 1/4, 1/5, 1/6, 1/7, 1/9, 1/11, 1/13 or 1/15, and the like, and the migration number of lithium ions in the single ion conductor polymer solid electrolyte membrane is not less than 0.5, and the ionic conductivity is not less than 1 x 10-5S/cm. Preferably, the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component may be 1: (3-12), thereby further contributing to the improvement of the transference number and ionic conductivity of lithium ions in the single ion conductor polymer solid electrolyte membrane. Further, the inventors have found that if the mass ratio of the lithium-containing monomer to the crosslinking monomer is too large, it is not favorable for the crosslinking film formation of the polymer solid electrolyte, and if the mass ratio of the lithium-containing monomer to the crosslinking monomer is too small, it is not favorable for improving the transference number and ionic conductivity of lithium ions in the solid electrolyte film; if the amount of the polymer is too small, the effect of improving the film forming property and the mechanical property of the solid electrolyte membrane is not obvious, and if the amount of the polymer is too large, the transmission efficiency of lithium ions in the solid electrolyte membrane is also influenced, and the conductivity of the solid electrolyte membrane is also influenced. In the invention, by comprehensively controlling the lithium-containing monomer, the crosslinking monomer, the polymer and the lithium salt to be in the above proportioning range, the single-ion conductor polymer solid electrolyte membrane can be ensured to have higher lithium ion conductivity and lithium ion migration number, so that the lithium ion conductivity is 1 multiplied by 10-5S/cm or more and a lithium ion transport number of 0.5 or more.
According to the embodiments of the present invention, the inventors have also found that by incorporating a proper amount of inorganic particles into the single-ion conductor polymer solid electrolyte membrane of the present invention, not only can the mechanical properties of the solid electrolyte membrane be improved, but also the inorganic particles can interact with the polymer chain segment and the lithium salt of the solid electrolyte membrane to increase the transmission channel of lithium ions, and improve the conductivity and transference number of lithium ions; by doping a proper amount of plasticizer into the single-ion conductor polymer solid electrolyte membrane, not only can the dissociation of lithium salt be promoted, the transference number of lithium ions be increased, but also the ion conductivity of the polymer solid electrolyte membrane can be improved. However, if the amount of the inorganic particles or the plasticizer is too large, the conductivity of the solid electrolyte membrane is affected. According to the invention, by controlling the addition amount range of the inorganic particles and the plasticizer, the solid electrolyte membrane can be further ensured to have higher lithium ion conductivity, higher lithium ion migration number and good mechanical property.
According to an embodiment of the present invention, a single ion conductor polymer solid electrolyte membrane may include: 10-40 parts by weight of lithium-containing monomer, 8-20 parts by weight of crosslinking monomer, 2-20 parts by weight of polymer, 0-10 parts by weight of plasticizer, 0-10 parts by weight of inorganic particles and lithium salt; wherein, the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component can be 1: (2-13); for example, the lithium-containing monomer may be 10, 15, 20, 25, 30, 35, or 40, etc., the crosslinking monomer may be 8, 10, 12, 14, 16, 18, or 20, etc., the polymer may be 2, 4, 6, 8, 10, 13, 16, or 19, etc., the plasticizer may be 1, 3, 5, 7, or 9, etc., the inorganic particle may be 2, 4, 6, 8, or 10, etc., and the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component may be 1/1, 1/3, 1/5, 1/7, 1/9, 1/11, or 1/12, etc. Therefore, the solid electrolyte membrane can be further ensured to have higher lithium ion conductivity, higher lithium ion transference number and good mechanical property.
According to the embodiment of the invention, the chemical repeating unit of the single-ion conductor polymer solid electrolyte membrane can be shown as formula 1, wherein x can be an integer of 2-40, y can be an integer of 2-50, and R1And R2May be each independently a hydrogen atom or a methyl group. The inventor finds that the lithium-containing monomer can contain amino, the crosslinking monomer can contain epoxy end group, the amino in the raw material component can react with sulfonic acid to generate sulfamide, part of the amino is changed from primary amine to secondary amine by controlling the reaction condition, the residual active hydrogen on the amino can continuously react with the crosslinking monomer containing epoxy end group, and the polymer with certain mechanical strength is obtained by curing, for example, the polymer has the structure shown in formula 1, thereby further ensuring that the solid electrolyte membrane has higher lithium ion conductivity and lithium ion conductivityThe transference number and the good mechanical property,
according to another embodiment of the present invention, the structural formula of the lithium-containing monomer can be represented by formula 2, wherein x can be an integer of 2-40, and R (corresponding to R in formula 1)1) The monomer with amino and epoxy end groups can not only be subjected to complex dissociation with lithium ions to conduct the lithium ions, but also can replace metal ions connected with sulfonate groups into the lithium ions through processes of water washing, replacement and the like, and finally part of lithium sulfonate is grafted on a polymer chain, so that the finally formed polymer solid electrolyte membrane can be ensured that the sulfonate groups are fixed on the chain and cannot move, only the lithium ions move in the charge and discharge process, and the transference number of the lithium ions of the solid electrolyte membrane is improved.
According to an embodiment of the present invention, the crosslinking monomer may include at least two epoxy groups, wherein the epoxy group may be at least one selected from ethoxy, propoxy, and butoxy groups. The inventor finds that the main chain in the monomer with the amine group and the epoxy end group can be complexed and dissociated with lithium ions to conduct the lithium ions, and the invention can further contribute to improving the transference number of the lithium ions in the solid electrolyte membrane by adopting the crosslinking monomer comprising at least two epoxy groups. It should be noted that the crosslinking monomer including at least two epoxy groups in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, and for example, the crosslinking monomer may be at least one selected from trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
According to the embodiment of the present invention, the type of the polymer in the present invention is not particularly limited, and those skilled in the art can select the polymer according to actual needs as long as the film forming property and the plasticity of the solid electrolyte membrane can be improved, for example, the polymer may be at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polycarbonate, and the selection of the above-mentioned kind of polymer may further contribute to the improvement of the film forming property and the mechanical property of the solid electrolyte membrane.
According to the embodiment of the present invention, the kind of the inorganic particles in the present invention is not particularly limited, and those skilled in the art can select the inorganic particles according to actual needs, for example, the inorganic particles may be selected from Al2O3、SiO2Molecular sieves, Li1.5Al0.5Ge1.5P3O12And Li1.4Al0.4Ti1.6(PO4)3Thereby not only improving the mechanical properties of the solid electrolyte membrane, but also being more beneficial to improving the conductivity and transference number of lithium ions. Further, the average particle diameter of the inorganic particles in the present invention may be 5 to 600nm, for example, 5nm, 10nm, 20nm, 50nm, 100nm, 150nm, 200nm, 300nm, 400nm, or 500nm, and the inventors found that when the particle diameter of the inorganic particles is too large, the nano-property is not exhibited, but phase separation occurs with the polymer, and the interface impedance is increased to lower the ion conductivity of the solid electrolyte membrane; when the particle size of the inorganic particles is too small, the requirement on a dispersion process is high, and the inorganic particles are easy to agglomerate. According to the invention, by controlling the particle size of the inorganic particles within the addition range, the solid electrolyte membrane can be further ensured to have higher lithium ion conductivity, higher lithium ion migration number and good mechanical property.
According to the embodiment of the present invention, the kind of the plasticizer in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the plasticizer may be at least one selected from propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, tetraglyme, and succinonitrile, and the selection of the above kind of plasticizer is not only more beneficial to improving the transference number of lithium ions and the mechanical properties of the solid electrolyte membrane, but also has wide and easily available raw material sources.
According to the embodiment of the present invention, the thickness of the single ion conductor polymer solid electrolyte membrane may be 10 to 500 μm, for example, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, or 500 μm, and the like, and the inventors found that the smaller the thickness of the solid electrolyte membrane, the greater the difficulty of the manufacturing process and the inferior mechanical properties are, but if the thickness of the solid electrolyte membrane is too large, the energy density of the solid battery is affected, and by controlling the thickness of the solid electrolyte membrane to the above range, the solid electrolyte can have the superior mechanical properties, and the energy density of the solid battery can be further ensured when the solid electrolyte membrane is used in the solid battery. Preferably, the thickness of the solid electrolyte membrane may be 50 to 200 μm, whereby it may be further advantageous to improve the energy density of the solid-state battery.
In another aspect of the present invention, the present invention provides a method for preparing the above single-ion conductor polymer solid electrolyte membrane. According to an embodiment of the invention, the method comprises: (1) mixing lithium-containing monomers, crosslinking monomers, polymers, plasticizers, inorganic particles, lithium salts and organic solvents according to a preset ratio to obtain mixed slurry; (2) and coating the mixed slurry into a film, heating, polymerizing and curing so as to greatly improve the polymerization degree and the crosslinking degree of the raw material components and obtain the single-ion conductor polymer solid electrolyte membrane. The inventor finds that compared with the prior art, the method is simple and efficient, can be used for large-scale production in a coating mode, and the prepared composite solid polymer electrolyte membrane has higher ionic conductivity and lithium ion migration number, and can be widely applied to solid lithium batteries to reduce concentration polarization, improve discharge specific capacity and prolong cycle life. It should be noted that the features and effects described for the single-ion conductor polymer solid electrolyte membrane are also applicable to the method for preparing the single-ion conductor polymer solid electrolyte membrane, and are not described in detail herein.
According to the embodiment of the invention, a lithium-containing monomer, a crosslinking monomer, a polymer, a plasticizer and inorganic particles can be completely dissolved in advance, lithium salt is added and uniformly dispersed to obtain a mixed slurry, wherein the solid content of the mixed slurry can be 10-50 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, and the inventors found that the solid content of the mixed slurry directly affects the viscosity and stability of the slurry, and the excessive or insufficient solid content is not beneficial to smooth coating.
According to the embodiment of the present invention, the solvent used in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the solvent may be at least one selected from acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, and acetone.
In yet another aspect of the invention, a solid state lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes a positive electrode, a negative electrode, and the single ion conductor polymer solid electrolyte membrane described above or the single ion conductor polymer solid electrolyte membrane obtained by the method for producing a single ion conductor polymer solid electrolyte membrane described above. Compared with the prior art, the solid-state lithium battery has the advantages that the discharge specific capacity and the charge-discharge efficiency are improved, the stability and the electrochemical cycle performance are higher, the service life is longer, and the commercial prospect is good. It should be noted that the features and effects described for the single-ion conductor polymer solid electrolyte membrane and the method for preparing the single-ion conductor polymer solid electrolyte membrane are also applicable to the solid lithium battery, and are not repeated herein.
According to an embodiment of the present invention, the type of the solid lithium battery in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the solid lithium battery may be a lithium metal battery, wherein the active material of the positive electrode thereof may include at least one selected from lithium iron phosphate, lithium cobaltate, and lithium nickel cobalt manganese oxide, and the negative electrode thereof may be lithium metal.
For a further understanding of the contents and advantages of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Synthesis of lithium-containing monomer having structure of formula 2
First 0.35g sodium dodecyl sulfate was dissolved in 10mL disodium hydrogen phosphate buffer solution (pH 4.5); then adding 10mM of polyetheramine, and stirring continuously until the polyetheramine is completely dissolved; and finally, adding 0.5U/mL laccase as a catalyst to initiate polymerization reaction. And putting the reaction container into a freezer with the temperature of 5 ℃, and standing for more than 24 hours. During the reaction process, the suspension is subjected to ultraviolet and visible light tests, and the reaction process is monitored. After the reaction is finished, acetone (10mL) with the same volume is added into the reaction liquid for demulsification, the obtained precipitate is collected by centrifugation and filtration, and is washed by acetone and deionized water to remove oligomers and other impurities. And (3) drying the final product in a drying oven at 60 ℃ to obtain the end group modified sodium polyether imide sulfonate.
Fully dissolving the dried terminal group modified sodium polyether imide sulfonate in N, N-dimethylformamide, preparing a solution with a certain concentration, standing in vacuum for 24h for defoaming, casting the solution on a clean glass plate to form a film, drying at 60 ℃ for 24h, cooling to room temperature, and taking out. The cast film was placed in 0.5mol/L H at room temperature2SO4In the solution, every 6H, new 0.5mol/L H is replaced2SO4Soaking the solution for 48 hours, washing the membrane to neutrality by using deionized water, and then soaking the membrane in saturated Li2CO3In solution, saturated Li is replaced by new saturated Li at intervals of 6h2CO3And soaking the solution at room temperature for 48h, washing the membrane to be neutral by using deionized water, and drying at 80 ℃ for 24h to obtain the end group modified lithium polyether imide sulfonate.
(2) Preparation of single ion conductor polymer solid electrolyte membrane
Prepared from the above 10gLithium-containing monomer, 4g of crosslinked monomer trimethylolpropane triglycidyl ether, 6g of lithium ion-conducting polymer polyethylene oxide (PEO), 6g of plasticizer tetraethylene glycol dimethyl ether, 2g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:6 to EO groups in the polymer and the monomer to obtain slurry; coating the slurry into a film, curing the film into a film by thermally initiating free radical polymerization, heating the film at 80 ℃, volatilizing the solvent and carrying out crosslinking curing to obtain the single-ion conductor polymer solid electrolyte film.
Morphology characterization of single-ion conductor polymer solid electrolyte membrane
The surface of the single-ion conductor polymer solid electrolyte membrane is observed by a scanning electron microscope, and the SEM is shown in figure 1, so that the electrolyte membrane is uniform, compact and nonporous.
Lithium ion conductivity test
Forming an ss/single-ion conductor polymer solid electrolyte/ss blocking battery by using a stainless steel sheet and a single-ion conductor polymer solid electrolyte (thickness l, area S), packaging by using a CR2016 button battery, testing an EIS map obtained at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ to obtain alternating current impedance, testing the frequency range of 0.1-1000 kHz under the condition of 5mV disturbance voltage, and fitting to obtain the bulk resistance R of the single-ion conductor polymer solid electrolyte at different temperaturesbThen according to the formula sigma ═ l/(R)bxS) to obtain the lithium ion conductivity sigma of the solid polymer electrolyte, the test result is shown in figure 2, and the lithium ion conductivity of the single-ion conductor polymer solid electrolyte prepared in figure 2 can reach 1 x 10 at 30-40 DEG C-4S/cm, and as the temperature rises, the lithium ion conductivity of the lithium ion battery is further improved.
Transference number test of lithium ion
A Li// single-ion conductor polymer solid electrolyte// Li non-blocking battery is formed by a lithium sheet and a single-ion conductor polymer solid electrolyte, and is packaged by a CR2016 button battery, wherein the test temperature is 70 ℃, and the frequency range is 0.1-1000 kHz. Method for testing initial current I under polarization voltage by using timing current method0And steady-state current Is, and the resistance to lithium interface reaction before and after polarization Is tested by adopting an alternating-current impedance method. Is calculated by the formula
Wherein Io Is initial current, Is steady-state current, V Is polarization voltage, 10mV Is taken, Ro Is reaction resistance to the lithium interface before polarization, and Rs Is reaction resistance to the lithium interface after polarization. The test results are shown in FIG. 3, and the current I before and after polarization can be obtained from the main graph0And ISThe reaction resistance of the interface before and after polarization can be obtained from the upper right side subpicture, and the transference number of the lithium ion can be calculated to be 0.7 by the calculation formula and is at a higher level in the polymer solid electrolyte.
(3) Application of single-ion conductor polymer solid electrolyte membrane
The anode active material is selected from lithium iron phosphate (LiFePO)4) The conductive agent is Super P, the binder is polyvinylidene fluoride (PVDF), and LiFePO is adopted according to the mass ratio4: super P: PVDF 8: 1:1, mixing the mixture in N-methylpyrrolidone (NMP) to obtain positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and carrying out vacuum drying at 110 ℃ for 24 hours to obtain a positive electrode piece. The lithium ion button cell is assembled in a glove box filled with argon by using the anode material, a metal lithium counter electrode and a single ion conductor polymer solid electrolyte membrane, and the performance of the cell is tested in a cell test system. The test temperature is 70 ℃, and the charge-discharge current density is set to be 0.2mA/cm2The discharge cut-off voltage is limited to 2.5-3.7V.
Comparative example 1
Dissolving a polymer polyethylene oxide (PEO) for leading lithium ions into acetonitrile, wherein the concentration of the polymer polyethylene oxide is 8%, then adding lithium salt LiTFSi, the molar ratio of the lithium salt LiTFSi to EO groups is 1:10, fully and uniformly mixing, coating the mixture on a release film, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte film. And assembling the lithium iron phosphate anode and the lithium metal cathode into a button cell, and testing the charge and discharge performance. The charge and discharge performance of the assembled button cell after approximately 50 cycles of charge and discharge cycle was measured by the same method as in example 1.
Example 2
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
27g of the above-prepared lithium-containing monomer, 15g of a crosslinking monomer trimethylolpropane triglycidyl ether, 15g of a lithium ion-conducting polymer polyethylene oxide (PEO), 10g of a plasticizer tetraethylene glycol dimethyl ether, 7.5g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:8 to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer to obtain slurry.
Example 3
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
10g of the above-prepared lithium-containing monomer, 20g of a crosslinking monomer trimethylolpropane triglycidyl ether, 2g of a lithium ion-conducting polymer polyethylene oxide (PEO), 10g of a plasticizer tetraethylene glycol dimethyl ether, 10g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:16 to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer to obtain slurry.
Example 4
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
40g of the above-prepared lithium-containing monomer, 10g of a crosslinking monomer trimethylolpropane triglycidyl ether, 25g of a lithium ion-conducting polymer polyethylene oxide (PEO), 15g of a plasticizer tetraethylene glycol dimethyl ether, 3g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:5 to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer to obtain slurry.
Example 5
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
60g of the above-prepared lithium-containing monomer, 5g of a crosslinking monomer trimethylolpropane triglycidyl ether, 10g of a lithium ion-conducting polymer polyethylene oxide (PEO), 5g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:6 to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer to obtain slurry.
Example 6
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
5g of the above-prepared lithium-containing monomer, 35g of a crosslinking monomer trimethylolpropane triglycidyl ether, 25g of a lithium ion-conducting polymer polyethylene oxide (PEO), 6g of a plasticizer tetraethylene glycol dimethyl ether, 2g of inorganic particles Li1.5Al0.5Ge1.5P3O12Respectively dissolving and uniformly dispersing the lithium salt LiTFSi into an acetonitrile solvent in advance, and adding the lithium salt LiTFSi into the acetonitrile solvent in a molar ratio of 1:9 to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer to obtain slurry.
Comparative example 2
The difference from example 1 is that:
(2) preparation of single ion conductor polymer solid electrolyte membrane
The addition ratio of the lithium salt LiTFSi to EO groups (namely lithium ion complex dissociation groups) in the polymer and the monomer is 1: 20.
The lithium ion conductivity and the lithium ion transport number of the single ion conductor polymer solid electrolyte membranes prepared in examples 1 to 6 and comparative examples 1 to 2 were measured by the same method as in example 1, and the results are shown in table 1. It can be seen that the transference number of lithium ions of the solid electrolyte membrane is generally less than 0.2 and the ionic conductivity is 10 by using the traditional PEO system-6An order of magnitude; to adopt the bookThe ionic conductivity of the single-ion conductor polymer electrolyte membrane prepared in the application example is 10 at 30 DEG C-5In the above way, the transference number of lithium ions is obviously improved; in addition, when the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is too small, the improvement of the lithium ion conductivity and the lithium ion transport number of the single-ion conductor polymer solid electrolyte membrane can be influenced, and particularly, the influence on the lithium ion transport number is more remarkable.
TABLE 1 examples and comparative examples solid electrolyte Membrane Electrical Properties
The solid-state batteries of the single-ion conductor polymer solid electrolyte membranes prepared in the example 1 and the comparative example 1 are subjected to charge and discharge tests by the same method as the example 1, wherein the specific discharge capacity and the charge and discharge efficiency of the example 1 and the comparative example 1 are shown in fig. 4, and it can be seen that after charge and discharge cycles are about 50 circles, compared with the comparative example 1, the solid-state lithium metal battery assembled by the single-ion conductor polymer solid-state electrolyte in the example 1 of the invention has the specific discharge capacity of 140mAh/g, the charge and discharge efficiency of nearly 97%, and the charge and discharge performance is better.
By contrast, the single-ion conductor polymer solid electrolyte membrane with the raw material composition and the proportion of the invention has better lithium ion conductivity and lithium ion migration number, and the prepared solid battery has excellent charge and discharge performance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A single ion conductor polymer solid electrolyte membrane, comprising:
5-50 parts by weight of lithium-containing monomer, 5-25 parts by weight of crosslinking monomer, 1-30 parts by weight of polymer, 0-20 parts by weight of plasticizer, 0-15 parts by weight of inorganic particles and lithium salt;
wherein the molar ratio of the lithium salt to the sum of the lithium ion complex dissociation groups in each component is 1: (1-16).
2. The single ion conductor polymer solid electrolyte membrane according to claim 1, wherein the chemical repeating unit of the single ion conductor polymer solid electrolyte membrane is represented by formula 1, wherein x is an integer of 2 to 40, y is an integer of 2 to 50, and R is1And R2Each independently is a hydrogen atom or a methyl group,
3. the single-ion conductor polymer solid electrolyte membrane according to claim 1, wherein the structural formula of the lithium-containing monomer is shown as formula 2, wherein x is an integer of 2 to 40, R is a hydrogen atom or a methyl group,
4. the single ion conductor polymer solid electrolyte membrane according to claim 1, wherein the crosslinking monomer comprises at least two epoxy groups, the epoxy groups being at least one selected from ethoxy, propoxy, and butoxy groups;
optionally, the crosslinking monomer is at least one selected from trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
5. The single ion conductor polymer solid electrolyte membrane according to claim 1, wherein at least one of the following conditions is satisfied:
the polymer is at least one selected from polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate and polycarbonate;
the inorganic particles are selected from Al2O3、SiO2Molecular sieves, Li1.5Al0.5Ge1.5P3O12And Li1.4Al0.4Ti1.6(PO4)3At least one of;
the average particle diameter of the inorganic particles is 5-600 nm;
the plasticizer is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, tetraglyme, and succinonitrile.
6. The single ion conductor polymer solid electrolyte membrane according to claim 1, wherein at least one of the following conditions is satisfied:
the thickness of the single-ion conductor polymer solid electrolyte membrane is 10-500 mu m;
the lithium ion conductivity of the single-ion conductor polymer solid electrolyte membrane is not less than 1 x 10-5S/cm, and the transference number of lithium ions is not less than 0.5.
7. A method of preparing the single ion conductor polymer solid electrolyte membrane according to any one of claims 1 to 6, comprising:
(1) mixing lithium-containing monomers, crosslinking monomers, polymers, plasticizers, inorganic particles, lithium salts and organic solvents according to a preset ratio to obtain mixed slurry;
(2) and coating the mixed slurry into a film, and heating, polymerizing and curing to obtain the single-ion conductor polymer solid electrolyte membrane.
8. The method of claim 7, wherein at least one of the following conditions is satisfied:
the solid content of the mixed slurry is 10-50 wt%;
the solvent is at least one selected from acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and acetone.
9. A solid state lithium battery, comprising:
a positive electrode;
a negative electrode; and
the single ion conductor polymer solid electrolyte membrane of any one of claims 1 to 6 or prepared by the method of any one of claims 7 to 8.
10. The solid-state lithium battery according to claim 9, wherein the active material of the positive electrode includes at least one selected from lithium iron phosphate, lithium cobaltate, and lithium nickel cobalt manganese oxide, and the negative electrode is a lithium metal.
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