CN111211349B - Mixed ion electron conductive polymer-based interface layer and preparation method and application thereof - Google Patents

Mixed ion electron conductive polymer-based interface layer and preparation method and application thereof Download PDF

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CN111211349B
CN111211349B CN201811394930.4A CN201811394930A CN111211349B CN 111211349 B CN111211349 B CN 111211349B CN 201811394930 A CN201811394930 A CN 201811394930A CN 111211349 B CN111211349 B CN 111211349B
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CN111211349A (en
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胡勇胜
张强强
邵元骏
刘丽露
陈立泉
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    • H—ELECTRICITY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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Abstract

The embodiment of the invention relates to a mixed ion electron conducting polymer-based interface layer of a solid electrolyte, a preparation method and application thereof, wherein the mixed ion electron conducting polymer-based interface layer is a composite material of a polymer material, a carbon material and/or a carbon-based material and an alkali metal salt on an interface where the solid electrolyte is contacted with an alkali metal negative electrode of a battery; wherein the polymeric material comprises: one or more of PEO, PVDF, PPC, PVP, PVDF-HFP; the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; alkali metal salts include: LiClO4、LiPF6、LiBOB、CF3SO3Li、F2NLiO4S2、C2F6NO4S2One or more of lithium salts of Li, or NaClO4、NaPF6、CF3SO3Na、F2NNaO4S2、C2F6NO4S2One or more of the sodium salts of Na.

Description

Mixed ion electron conductive polymer-based interface layer and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a mixed ion electronic conducting polymer-based interface layer of a solid electrolyte, a preparation method and application thereof.
Background
The demand of high-speed economic development on energy sources is continuously increased, the progress of the society arouses the eager attention of human beings on the environment, and batteries attract the wide attention of the whole society as a green and environment-friendly renewable energy source storage form. At present, various portable small-sized electronic devices, passenger vehicles and the like widely adopt traditional lithium ion batteries as energy storage devices, and in the fields of larger-scale energy storage and power batteries, the traditional lithium ion batteries using flammable organic liquid electrolyte have huge potential safety hazards. The research and development of a new generation of battery with high safety coefficient and high energy density becomes a requirement for social development.
Among various battery systems, solid-state batteries are widely recognized by researchers as the most promising new-generation battery system. The solid-state battery abandons a liquid electrolyte system in the traditional lithium ion battery, adopts solid electrolyte with high thermal stability and chemical stability and wide electrochemical window, not only solves the potential safety hazard of the lithium ion battery, but also can adopt an alkali metal cathode and a high-voltage anode, and greatly improves the energy density of the battery. However, there are many problems in the practical application of solid-state batteries, and one of the main problems is the interfacial contact between the solid electrolyte and the alkali metal negative electrode. In order to solve the problem, various mechanisms such as different scientific research units and companies in the world propose various solutions, for example, interface layers such as zinc oxide, aluminum oxide, magnesium, tin, germanium, gold and the like are introduced between the solid electrolyte and the alkali metal cathode, but the interface layers have high raw material price, expensive instruments, complex operation and difficult realization of large-scale application. Therefore, it is necessary to develop a novel interface layer with cheap raw materials, cheap instruments and equipment and simple operation method, and to improve the interface contact problem between the solid electrolyte and the alkali metal cathode.
Disclosure of Invention
The invention aims to provide a mixed ion electron conductive polymer interface layer of a solid electrolyte, a preparation method and application thereof, and the interface resistance of the solid electrolyte and alkali metal is reduced by the mixed ion electron conductive polymer interface layer.
To achieve the above object, the present invention provides a mixed ion electron conducting polymer-based interfacial layer of a solid electrolyte, comprising: the mixed ion electron conducting polymer interface layer is arranged on the interface of the solid electrolyte and the contact of the alkali metal cathode of the battery; the mixed ion electron conducting polymer interface layer is a composite material of a polymer material, a carbon material and/or a carbon-based material and an alkali metal salt;
wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Bis (trifluoromethylsulfonyl) imide lithium C2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na.
Preferably, the mixed ionic electronic conducting polymer interface layer is used for conducting the transmission of ions and electrons.
Preferably, the thickness of the mixed ion electron conductive polymer interface layer is 100nm to 100 μm.
Preferably, the solid electrolyte is a lithium ion conductor or a sodium ion conductor;
wherein the lithium ion conductor includes: a Garnet-type structure oxide, NASICON-type structure oxide, LISICON-type structure sulfide, perovskite-type structure oxide, or P2 phase layered oxide solid electrolyte;
the sodium ion conductor includes: NASICON typeStructural oxide, perovskite-structured oxide, beta-Al2O3Or a P2 phase layered oxide solid electrolyte.
Preferably, the alkali metal negative electrode includes: any one of metallic lithium, metallic sodium, metallic lithium alloy, or metallic sodium alloy.
In a second aspect, an embodiment of the present invention provides a method for preparing the mixed ion electron conducting polymer interface layer according to the first aspect, where the preparation method is a solution spin coating method, and the method includes:
polishing the surface of the solid electrolyte sheet;
mixing and stirring solid polymer material, solid carbon material and/or carbon material and alkali metal salt in a solvent to form a solution; wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
spin-coating the solution on the surface of the solid electrolyte sheet by using a spin coater, and evaporating the solvent to dryness, so that the mixed ion electron conducting polymer interface layer is formed on the surface of the solid electrolyte sheet;
wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Bis (trifluoromethylsulfonyl) imide lithium C2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na; the solvent is water, an organic solvent or ionic liquid.
In a third aspect, an embodiment of the present invention provides a method for preparing a mixed ion electron conducting polymer interface layer according to the first aspect, where the preparation method is a solution casting method, and includes:
polishing the surface of the solid electrolyte sheet;
mixing and stirring solid polymer material, solid carbon material and/or carbon material and alkali metal salt in a solvent to form a solution; wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
pouring the solution into a template of polytetrafluoroethylene, and evaporating the solvent to form a mixed ionic-electronic conductive polymer film;
cutting out polymer films with corresponding sizes to cover the surfaces of the solid electrolyte sheets according to the sizes of the solid electrolyte sheets to form the mixed ion electron conductive polymer interface layers;
wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Lithium bis (trifluoromethylsulfonyl) imideC2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na; the solvent is water, an organic solvent or ionic liquid.
In a fourth aspect, embodiments of the present invention provide a solid electrolyte comprising a mixed ion electron conducting polymer interfacial layer as described in the first aspect above.
In a fifth aspect, embodiments of the present invention provide a battery including the solid electrolyte according to the fourth aspect.
The mixed ion electronic conducting polymer interface layer of the solid electrolyte provided by the embodiment of the invention is a key technology in the preparation process of a novel solid-state battery, the preparation method is simple, the interface resistance of the solid electrolyte and alkali metal can be effectively reduced, the energy density and the power density of the prepared solid-state battery are improved, and the application prospect is wide.
Drawings
FIG. 1 is a flow chart of a method for forming a mixed-ion-electron-conducting polymer interfacial layer according to an embodiment of the present invention;
FIG. 2 is a flow chart of another method for forming a mixed-ion-electron-conducting polymer interfacial layer according to an embodiment of the present invention;
FIG. 3 is an electrochemical impedance spectrum of an untreated NASICON structure sodium ion conductor ceramic sheet/sodium metal symmetrical battery provided by an embodiment of the invention;
FIG. 4 is an electrochemical impedance spectrum of a pure ion conducting polymer interface layer processed NASICON structure sodium ion conductor ceramic sheet/metal sodium symmetrical battery provided by an embodiment of the invention;
FIG. 5 is an electrochemical impedance spectrum of a NASICON structure sodium ion conductor ceramic sheet/metal sodium symmetric battery with mixed ion electron conducting polymer interface layer treatment provided by an embodiment of the invention;
FIG. 6 is a comparison of the three electrochemical impedance spectra of FIGS. 3, 4 and 5 provided by an embodiment of the present invention;
FIG. 7 is an electrochemical impedance spectrum of an untreated garnet-structured lithium ion conductor ceramic sheet/lithium metal symmetric battery provided in an embodiment of the present invention;
fig. 8 is an electrochemical impedance spectrum of a garnet-structured lithium ion conductor ceramic sheet/lithium metal symmetric battery processed by a mixed ion electron conducting polymer interface layer according to an embodiment of the present invention;
FIG. 9 is a comparison of the two electrochemical impedance spectra of FIGS. 7 and 8 provided by an embodiment of the present invention;
fig. 10 is a dc polarization plot of a hybrid ion-electron conducting polymer interfacial layer/stainless steel symmetric cell provided by an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
The mixed ion electronic conducting polymer interface layer of the solid electrolyte provided by the embodiment of the invention has the thickness of 100 nm-100 mu m on the interface of the solid electrolyte and the contact of the alkali metal negative electrode of the battery. The mixed ion electron conductive polymer interface layer is used for conducting the transmission of ions and electrons. The mixed ion electron conducting polymer interface layer is a composite material of a polymer material, a carbon material and/or a carbon-based material and an alkali metal salt.
Wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; alkali metal salts include: lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium bis (oxalato) borate (LiBOB), lithium trifluoro methane sulfonate (CF)3SO3Li), lithium bis (fluorosulfonyl) imide (F)2NLiO4S2) Lithium bis (trifluoromethylsulfonyl) imide (C)2F6NO4S2Li), or sodium perchlorate (NaClO)4) Sodium hexafluorophosphate (NaPF)6) Sodium trifluoromethanesulfonate (CF)3SO3Na), sodium bis (fluorosulfonyl) imide (F)2NNaO4S2) Bis (trifluoromethylsulfonyl) imide sodium salt (C)2F6NO4S2Na) sodium salt.
The solid electrolyte is a lithium ion conductor or a sodium ion conductor;
wherein the lithium ion conductor includes: a Garnet-type structure oxide, NASICON-type structure oxide, LISICON-type structure sulfide, perovskite-type structure oxide, or P2 phase layered oxide solid electrolyte;
the sodium ion conductor includes: NASICON-type structure oxide, perovskite-structure oxide, beta-Al2O3Or a P2 phase layered oxide solid electrolyte.
The alkali metal negative electrode includes: any one of metallic lithium, metallic sodium, metallic lithium alloy, or metallic sodium alloy.
The mixed ion electron conducting polymer interface layer is positioned on the interface where the solid electrolyte is contacted with the alkali metal cathode of the battery, so that the interface resistance of the solid electrolyte and the alkali metal can be effectively reduced, the energy density and the power density of the prepared solid battery are improved, the method is a key technology in the preparation process of the novel solid battery, and the application prospect is wide.
The mixed ion electron conducting polymer interface layer of the solid electrolyte provided by the embodiment of the invention can be prepared by a solution spin coating method. As shown in detail in the steps of fig. 1. The method mainly comprises the following steps:
step 110, polishing the surface of the solid electrolyte sheet;
step 120, mixing and stirring a solid polymer material, a solid carbon material and/or a carbon-based material and an alkali metal salt in a solvent uniformly to form a solution;
wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
and 130, spin-coating the solution on the surface of the solid electrolyte sheet by using a spin coater, and evaporating the solvent to dryness, so that a mixed ion electron conducting polymer interface layer is formed on the surface of the solid electrolyte sheet.
The materials used have been described previously and will not be repeated here.
The mixed ion electron conducting polymer interface layer of the solid electrolyte provided by the embodiment of the invention can be prepared by a solution casting method. As shown in detail in the steps of fig. 2. The method mainly comprises the following steps:
step 210, polishing the surface of the solid electrolyte sheet;
step 220, mixing and stirring solid polymer materials, solid carbon materials and/or carbon materials and alkali metal salt in a solvent uniformly to form a solution;
wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
step 230, pouring the solution into a template of polytetrafluoroethylene, and evaporating the solvent to dryness to form a mixed ionic-electronic conductive polymer film;
and 240, cutting out a polymer film with a corresponding size to cover the surface of the solid electrolyte sheet according to the size of the solid electrolyte sheet to form the mixed ion electron conductive polymer interface layer.
The materials used have been described previously and will not be repeated here.
In a specific example 1, the mixed ion electron conducting polymer interfacial layer was prepared by the solution spin coating method described above.
Polished NASICON type sodium ion conductor Na3Zr2Si2PO12The surface of the ceramic wafer. Taking solid polymer polyethylene oxide PEO (molecular weight is 60 ten thousand) and solid carbon material carbon nano tubes CNTs and alkali metal salt sodium bis (fluorosulfonyl) imide (F)2NNaO4S2) Wherein oxygen in PEO is reacted with F2NNaO4S2The molar ratio of sodium to sodium is 20:1, and CNTs accounts for PEO and F2NNaO4S25 percent of the total mass of the CNTs, and evenly mixing and stirring in water to form 50wt percent of water solution;
the solution was coated on NASICON type sodium ion conductor Na using a spin coater3Zr2Si2PO12Spin coating the surface of the ceramic chip, and evaporating the solvent at 55 ℃ to dryness to form the required mixed ion-electron conducting polymer interface layer.
The mixed ion electron conductive polymer interface layer is applied to the interface layer of the solid electrolyte of the solid battery, the solid electrolyte with the mixed ion electron conductive polymer interface layer is assembled into the solid battery, and the performance test is as follows:
2032 button cells were prepared and electrochemical impedance spectroscopy tests were performed on the cells of the invention with the solid electrolyte of the mixed ionic electronic conducting polymer interfacial layer. The specific assembling steps are that alkali metal is made into a wafer with the diameter of 16mm and the thickness of 300 mu m, the wafer is pasted on two sides of a solid electrolyte ceramic wafer and is packaged in a button type battery case, and alternating current impedance spectrum test is carried out. The frequency range is 1MHz-10 mHz.
The NASICON type sodium ion conductor Na is adopted3Zr2Si2PO12And (3) taking the ceramic chip as a solid electrolyte, and carrying out interface treatment according to the solution spin-coating method to obtain a mixed ion electron conducting polymer interface layer. And comparing the untreated ceramic wafer with the ceramic wafer using a pure ion-conducting polymer as an interface layer. The sodium metal is used as an alkali metal, the button cell is prepared by referring to the preparation process of the 2032 button cell, the alternating current impedance is tested, the NASICON structure sodium ion conductor ceramic wafer is not processed, the electrochemical impedance spectrum of the sodium metal symmetric cell is shown in figure 3, the pure ion conducting polymer is used as an interface layer to process the NASICON structure sodium ion conductor ceramic wafer, the electrochemical impedance spectrum of the sodium metal symmetric cell is shown in figure 5, the NASICON structure sodium ion conductor ceramic wafer is processed by the mixed ion electronic conducting polymer interface layer, and the electrochemical impedance spectrum of the sodium metal symmetric cell is shown in figure 5. For ease of comparison, we compared the two circuits of fig. 3, 4 and 5The chemical impedance spectra are superimposed to form fig. 6, so that the interface impedance of the interface layer processed by the mixed ion electron conducting polymer is visually compared with the interface impedance of the untreated and pure ion conducting polymer.
In another specific example 2, a mixed ion electron conducting polymer interfacial layer was prepared using the above solution casting apparatus.
Polished Garnet type lithium ion conductor Li7La3Zr2O12The surface of the ceramic wafer; taking solid polymer polyethylene oxide PEO (molecular weight is 60 ten thousand) and solid carbon material carbon nano tubes CNTs and alkali metal salt lithium bis (trifluoromethyl sulfonyl) imide (C)2F6NO4S2Li), where oxygen in PEO is reacted with C2F6NO4S2The molar ratio of lithium in Li is 20:1, and CNTs account for PEO and F2NNaO4S25 percent of the total mass of the CNTs, and evenly mixing and stirring in water to form 50wt percent of water solution; pouring the solution into a template of polytetrafluoroethylene, and evaporating the solvent to form a mixed ionic-electronic conductive polymer film; according to the Garnet type lithium ion conductor Li7La3Zr2O12Cutting out the polymer film with the corresponding size on the surface of the solid electrolyte sheet according to the size of the ceramic sheet to form the interface layer of the required mixed ion electron conductive polymer.
The mixed ion electron conductive polymer interface layer is applied to the interface layer of the solid electrolyte of the solid battery, the solid electrolyte with the mixed ion electron conductive polymer interface layer is assembled into the solid battery, and the performance test is as follows:
2032 button cells were prepared and electrochemical impedance spectroscopy tests were performed on the cells of the invention with the solid electrolyte of the mixed ionic electronic conducting polymer interfacial layer. The details are the same as in example 1 above.
The above-mentioned Garnet-type lithium ion conductor Li7La3Zr2O12And (3) taking the ceramic chip as a solid electrolyte, carrying out interface treatment according to a solution pouring method to obtain a mixed ion electron conductive polymer interface layer, and comparing by using an untreated ceramic chip. Using metallic lithium as alkali metal, ginsengThe button cell is prepared according to the preparation process of the 2032 button cell, the alternating current impedance is tested, the Garnet structure lithium ion conductor ceramic wafer is not processed, the electrochemical impedance spectrum of the lithium metal symmetrical cell is shown in figure 7, the mixed ion electronic conducting polymer interface layer is processed with the Garnet structure lithium ion conductor ceramic wafer, and the electrochemical impedance spectrum of the lithium metal symmetrical cell is shown in figure 8. For comparison, we superimposed the two electrochemical impedance spectra of fig. 7 and 8 to form fig. 9, so as to visually see the comparison of the interface treated and untreated with the mixed ion electron conducting polymer interface layer.
As can be seen from fig. 5 and 8, by using the mixed ion-electron conducting polymer interface layer provided by the present invention, the interface resistance between the solid electrolyte and the alkali metal is smaller, so that the solid-state battery can obtain higher energy density and power density, which plays a key role in improving the performance of the battery.
The mixed ionic electronic conducting polymer slurry in the example 1 is taken and poured into a polytetrafluoroethylene template, the solvent is evaporated to dryness to form a film, then a 16.2mm wafer is punched out of the film to prepare a 2032 button cell, and the direct current polarization test is carried out on the cell with the mixed ionic electronic conducting polymer. The specific assembly steps are that a stainless steel wafer with the diameter of 16mm is attached to two sides of a wafer made of a mixed ion electronic conducting polymer with the thickness of 200 mu m and the diameter of 16.2mm, and the wafer is packaged in a button type battery shell for direct current polarization test. The voltage was 20 mV. The measured DC polarization curve is shown in FIG. 10, and the electron conductivity can be calculated to be 4.8 × 10 according to the obtained data-6Ω-1cm-1The result shows that the mixed ion electron conductive polymer interface layer has good electron conductivity.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A mixed ion electron conducting polymer-based interfacial layer of a solid electrolyte, wherein the mixed ion electron conducting polymer interfacial layer is at an interface where the solid electrolyte contacts an alkali metal negative electrode of a battery; the mixed ion electron conducting polymer interface layer is a composite material of a polymer material, a carbon material and/or a carbon-based material and an alkali metal salt;
wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Bis (trifluoromethylsulfonyl) imide lithium C2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na;
the mixed ion electron conductive polymer interface layer is used for conducting transmission of ions and electrons.
2. The interfacial layer of mixed ion electron conducting polymer according to claim 1, wherein the thickness of the interfacial layer of mixed ion electron conducting polymer is 100nm to 100 μm.
3. The mixed-ion electronically conductive polymer interfacial layer of claim 1, wherein said solid electrolyte is a lithium-ion conductor or a sodium-ion conductor;
wherein the lithium ion conductor includes: a Garnet-type structure oxide, NASICON-type structure oxide, LISICON-type structure sulfide, perovskite-type structure oxide, or P2 phase layered oxide solid electrolyte;
the sodium ion conductor includes: NASICON-type structure oxide, perovskite-structure oxide, beta-Al2O3Or a P2 phase layered oxide solid electrolyte.
4. The mixed-ion electronically conductive polymer interfacial layer of claim 1, wherein the alkali metal negative electrode comprises: any one of metallic lithium, metallic sodium, metallic lithium alloy, or metallic sodium alloy.
5. A method of forming a mixed-ion-electron-conducting polymer interfacial layer according to any one of claims 1 to 4, wherein the method is a solution spin coating method comprising:
polishing the surface of the solid electrolyte sheet;
mixing and stirring solid polymer material, solid carbon material and/or carbon material and alkali metal salt in a solvent to form a solution; wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
spin-coating the solution on the surface of the solid electrolyte sheet by using a spin coater, and evaporating the solvent to dryness, so that the mixed ion electron conducting polymer interface layer is formed on the surface of the solid electrolyte sheet;
wherein the polymeric material comprises: one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polypropylene carbonate (PPC), polyvinylpyrrolidone (PVP) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP); the carbon material includes: natural graphite, artificial graphite, graphite micro-sheet, acetylene blackOne or more of carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Bis (trifluoromethylsulfonyl) imide lithium C2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na; the solvent is water, an organic solvent or ionic liquid.
6. A method of forming a mixed-ion electronically conducting polymer interfacial layer according to any one of claims 1 to 4, wherein said method is a solution casting method comprising:
polishing the surface of the solid electrolyte sheet;
mixing and stirring solid polymer material, solid carbon material and/or carbon material and alkali metal salt in a solvent to form a solution; wherein the mass ratio of each material is as follows: carbon material and/or carbon-based material: alkali metal salts: the polymer material is (1-10): 100;
pouring the solution into a template of polytetrafluoroethylene, and evaporating the solvent to form a mixed ionic-electronic conductive polymer film;
cutting out polymer films with corresponding sizes to cover the surfaces of the solid electrolyte sheets according to the sizes of the solid electrolyte sheets to form the mixed ion electron conductive polymer interface layers;
wherein the polymeric material comprises: polyethylene oxide PEO, polyvinylidene fluoride PVDF, polypropylene carbonateOne or more of vinyl ester PPC, polyvinylpyrrolidone PVP and polyvinylidene fluoride-hexafluoropropylene PVDF-HFP; the carbon material includes: one or more of natural graphite, artificial graphite, graphite micro-sheets, acetylene black, carbon nanotubes, carbon fibers, graphene oxide, reduced graphene oxide or amorphous carbon; the carbon-based material includes: a carbon-based material containing an organic group of an alkyl group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, an alkenyl group, or an alkynyl group; the alkali metal salts include: lithium perchlorate LiClO4Lithium hexafluorophosphate LiPF6Lithium bis (oxalato) borate LiBOB and lithium trifluoromethane sulfonate CF3SO3Li, bis (fluorosulfonyl) imide lithium F2NLiO4S2Bis (trifluoromethylsulfonyl) imide lithium C2F6NO4S2One or more of lithium salts of Li, or sodium perchlorate NaClO4Sodium hexafluorophosphate NaPF6Sodium triflate CF3SO3Na, bis (fluorosulfonyl) imide sodium F2NNaO4S2Bis (trifluoromethylsulfonyl) imide sodium salt C2F6NO4S2One or more of the sodium salts of Na; the solvent is water, an organic solvent or ionic liquid.
7. A solid electrolyte comprising the mixed ion electron conducting polymer interface layer according to any one of claims 1 to 4.
8. A battery comprising the solid electrolyte according to claim 7.
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