CN108539259B - Sodium perfluorofluoride polymer electrolyte, preparation method and application thereof, all-solid-state sodium ion battery and friction nano-generator system - Google Patents
Sodium perfluorofluoride polymer electrolyte, preparation method and application thereof, all-solid-state sodium ion battery and friction nano-generator system Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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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Abstract
The invention relates to the field of sodium ion batteries, and discloses a perfluorinated sodium polymer electrolyte, a preparation method and application thereof, an all-solid-state sodium ion battery and a friction nano generator system, wherein the method for preparing the perfluorinated sodium polymer electrolyte comprises the following steps: mixing the perfluorinated sulfonic acid resin with Na+The solution of (a) is subjected to ion exchange. The all-solid-state sodium ion battery provided by the invention contains the perfluorinated sodium polymer electrolyte, and has excellent safety and higher energy density compared with a battery using a liquid electrolyte.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a method for preparing a sodium perfluoropolymer electrolyte, the sodium perfluoropolymer electrolyte prepared by the method, application thereof, an all-solid-state sodium ion battery and a friction nano-generator system.
Background
With the consumption of a large amount of fossil energy and the increasing pollution to the environment, it is highly necessary to develop new energy technologies to replace the conventional fossil energy.
In recent years, various principles and prototypes of mechanical energy capture have been reported in succession, including electrostatic and triboelectric effects, electromagnetic effects and piezoelectric effects.
In particular, professor wangzhining et al developed triboelectric nano-generators (TENGs) based on the tribological effect and the electrostatic induction coupling mechanism. TENGs may be used to capture various mechanical energies, such as wind energy, rain energy, and air flow energy.
However, the energy captured by TENGs cannot provide a stable electrical energy output due to the randomness of the mechanical energy and the pulsed ac output characteristics of TENGs. Therefore, there is a strong need for efficient, stable energy storage devices to store electrical energy captured by triboelectric nanogenerators.
Large scale storage of electrical energy requires not only a sufficiently high storage capacity of the battery system, but also that the system is cost effective and environmentally friendly.
In recent years, sodium ion batteries have attracted much attention as electrical energy storage applications due to the abundant natural resources and low cost of sodium compared to lithium ion batteries.
However, sodium ion batteries still present significant challenges in terms of safety, lifetime, and power density, limiting the commercialization of conventional Sodium Ion Batteries (SIBs).
Therefore, in recent years, research on all-solid-state sodium ion batteries has been competitively conducted all over the world.
Disclosure of Invention
One of the objects of the present invention is to solve the problem of low safety due to flammability of a liquid electrolyte of an all-solid sodium ion battery, and to provide a solid perfluorosodium polymer electrolyte having high safety and capable of improving the cycle life of the battery and increasing the energy density, and an all-solid sodium ion battery comprising the solid perfluorosodium polymer electrolyte.
The invention aims to solve the problem that the energy captured by the conventional friction nano generator cannot provide stable electric energy output, and provides an energy storage device containing solid sodium perfluoropolymer electrolyte to store the electric energy captured by the friction nano generator and realize efficient and stable electric energy output.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a sodium perfluoropolymer electrolyte, comprising: mixing the perfluorinated sulfonic acid resin with Na+The solution of (a) is subjected to ion exchange.
In a second aspect, the present invention provides a sodium perfluoropolymer electrolyte prepared by the method of the first aspect.
In a third aspect, the present invention provides the use of the sodium perfluoropolymer electrolyte of the second aspect as an electrolyte for an all-solid-state sodium ion battery.
In a fourth aspect, the present invention provides an all-solid-state sodium ion battery comprising:
a solid electrolyte, the solid electrolyte being Na3P1-mAsmS4(0≤m≤0.5)、Na2O-11Al2O3、Na3Zr2Si2PO12、Na3PSe4、94Na3PS4-6Na4SiS4、Na3SbS4、50Na2S-50P2S5、60Na2S-40GeS2、50Na2S-50SiS2And a sodium perfluoropolymer electrolyte; and
and a negative electrode.
In a fifth aspect, the invention provides a friction nano-generator system, comprising the all-solid-state sodium-ion battery of the fourth aspect and a friction nano-generator, wherein the electric energy generated by the friction nano-generator is stored in the all-solid-state sodium-ion battery.
The all-solid-state sodium ion battery provided by the invention has excellent safety and higher energy density compared with a battery using a liquid electrolyte.
The all-solid-state sodium ion battery provided by the invention also has the advantage of long service life, can be applied to portable electronic devices, can also be used as a power supply of an electric vehicle or a fixed energy storage system, and has wide market prospect.
The all-solid-state sodium ion battery provided by the invention can reduce the requirement on packaging.
The friction nano generator system provided by the invention can store electric energy and can realize high-efficiency and stable electric energy output.
The friction nano generator system provided by the invention also has the advantages of low cost and environmental friendliness.
Drawings
FIG. 1 shows the results of the test of PFSA-Na-1 membrane, wherein (a) is the folded state of the PFSA-Na-1 membrane prepared in example 1; (b) restoring the state for it; (c) typical stress-strain relationship curves for the PFSA-Na-1 film prepared in example 1; (d) is an Arrhenius curve of PFSA-Na-1 membrane swollen in EC-PC mixed solvent.
Fig. 2 is a test result of the symmetric Na | PFSA-Na | Na battery of preparation example 3, in which (a) is a graph of current change with time after applying a dc voltage of 5 mv to the symmetric Na | PFSA-Na | Na battery of preparation example 3; (b) schematic of the sodium plating/stripping experiments for the symmetric Na | PFSA-Na | Na cell of preparation 3; (c) is at 0.2mA/cm2Voltage versus time curves during the sodium plating/stripping experiments for the symmetric Na | PFSA-Na | Na battery of preparation 3 at current density.
Fig. 3 is a test result of the all-solid battery of preparation example 3, in which (a) is a charge and discharge curve of the all-solid battery of preparation example 3 at different current densities; (b) the rate performance curve of the all-solid battery of preparation example 3 is shown; (c) the long-term cycle performance, capacity and coulombic efficiency of the all-solid-state battery of preparation example 3 were plotted as a function of cycle number at a current density of 5 mA/g; (d) the long-term cycling performance, capacity and coulombic efficiency of the all-solid-state battery of preparation example 3 were plotted against the number of cycles at a current density of 48 mA/g.
Fig. 4 is a test result of the friction nanogenerator system of preparation example 5, in which (a) is a schematic view of an apparatus for storing pulse energy collected by the friction nanogenerator system of preparation example 5 using an all-solid-state battery of preparation example 2; (b) a partial enlarged view of the triboelectric nanogenerator system of preparative example 5; (c) the open circuit voltage of the tribo nanogenerator system of preparation example 5 was plotted against time; (d) the change curve of the short-circuit current of the friction nano generator system of the preparation example 5 along with the time is shown; (e) the discharge curves of the battery after charging the all-solid-state battery of preparation example 3 with the tribo nanogenerator system of preparation example 5 at different current densities were shown.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing a sodium perfluoropolymer electrolyte, comprising: mixing perfluorosulfonic acid resin (PFSA) with Na+The solution of (a) is subjected to ion exchange.
Said Na-containing component+The solution (b) may be one or more of a sodium hydroxide solution, a sodium acetate solution, a sodium chloride solution, a sodium nitrate solution, and the like. The invention is to said Na-containing+The concentration of the solution of (a) is not particularly limited. For example, the compound contains Na+In the form of Na+The molar concentration can be 0.1-10 mol/L.
By the ion exchange, protons on PFSA are exchanged for Na+Obtaining PFSA-Na, namely the perfluorinated sodium polymer.
Preferably, the conditions of the ion exchange include: the temperature is 40-100 ℃, and the time is 6-24 h. The first contact may, for example, immerse the PFSA in a solution containing Na+In the solution of (1).
Preferably, the method further comprises: and washing and drying the product obtained after ion exchange in sequence. The washing may be performed with water (e.g., deionized water, etc.).
Preferably, the drying conditions include: in the presence of protective gas, the temperature is 5-45 ℃ and the time is 5 minutes to 1 hour. The shielding gas may be, for example, at least one of helium, neon, argon, and nitrogen.
Preferably, the method further comprises: after the drying, the dried sodium perfluoropolymer electrolyte is mixed with a mixed solvent containing ethylene carbonate and polycarbonate in the presence of a molecular sieve. The dried sodium perfluoropolymer electrolyte can be swollen by the mixing, thereby being obviously beneficial to providing the ionic conductivity of the sodium perfluoropolymer electrolyte.
Preferably, the mixing conditions include: the temperature is 5-45 ℃, and the time is 12-72 h.
The molecular sieve of the present invention is not particularly limited in kind as long as it is a molecular sieveA molecular sieve capable of achieving a moisture adsorption effect. For example, the molecular sieve may be
An active molecular sieve. The amount of the molecular sieve used in the present invention is not particularly limited, and those skilled in the art can select the amount according to the effect of the action in combination with the amount conventionally used in the art.
Preferably, the volume ratio of Ethylene Carbonate (EC) to Polycarbonate (PC) in the mixed solvent containing EC and PC is 1: (0.6-1.5). The amount of the mixed solvent used in the present invention is not particularly limited as long as the dried sodium perfluoropolymer electrolyte can be immersed in the mixed solvent.
In a second aspect, the present invention provides a sodium perfluoropolymer electrolyte prepared by the method of the first aspect.
In a third aspect, the present invention provides the use of the sodium perfluoropolymer electrolyte of the second aspect as an electrolyte of an all-solid-state sodium ion battery.
In a fourth aspect, the present invention provides an all-solid-state sodium ion battery comprising:
a solid electrolyte, the solid electrolyte being Na3P1-mAsmS4(0≤m≤0.5)、Na2O-11Al2O3(β -alumina), Na3Zr2Si2PO12、Na3PSe4、94Na3PS4-6Na4SiS4、Na3SbS4、50Na2S-50P2S5、60Na2S-40GeS2、50Na2S-50SiS2And a sodium perfluoropolymer electrolyte; and
and a negative electrode.
Preferably, the solid electrolyte is a sodium perfluoropolymer electrolyte according to the second aspect of the present invention.
The Na is2O-11Al2O3Namely β -aluminum oxide (Wen, Z.Y., Cao, J.D., Gu, Z.H).,Xu,X.X.,Zhang,F.L.Research on sodium sulphur battery for energy storage,Solid StateIonics 2008,179,1697-1701)。
Preferably, the positive electrode slurry for forming the positive electrode contains P2-type Na0.67NixMgyMn1-x-yO2(x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.2). Using Na containing P2-form0.67NixMgyMn1-x-yO2When the material is used as anode slurry and an all-solid-state sodium ion battery formed by using the solid electrolyte is used as an energy storage device of a friction nano-generator system, the energy generated by the friction nano-generator can be efficiently stored. The inventors of the present invention have found that other materials known in the art, such as Na, can be used3V2(PO4)3、NaMn0.44O2And NaFePO4When the materials are used as anode slurry, the performance of the capability of storing the energy generated by the friction nano generator is general, and only the material containing P2-type Na is adopted0.67NixMgyMn1-x-yO260% of the storage capacity of the material.
Preferably, said P2-form Na0.67NixMgyMn1-x-yO2The preparation method comprises the following steps:
1) dissolving a sodium source and EDTA in an aqueous solution under the condition of an alkaline solution to obtain a first solution;
2) mixing the first solution with a manganese source, a nickel source and a magnesium source to obtain a second solution;
3) mixing the second solution with citric acid and/or ethylene glycol to obtain a third solution;
4) forming the third solution into gel, and drying and roasting the gel in sequence.
Preferably, in the preparation of said P2-form Na0.67NixMgyMn1-x-yO2In the method of (1), EDTA, citric acid and said P2-form Na0.67NixMgyMn1-x-yO2The molar ratio of the total metal ions in the solution is 1: (1.05-2): (0.6-1.2).
Preferably, in the preparation of said P2-form Na0.67NixMgyMn1-x-yO2In the method of (1), in the step 3), when the second solution is mixed with citric acid and/or ethylene glycol, the pH value of the third solution is 5.5-6.8 by adding an alkaline substance into the solution.
The basic substance of the present invention may be, for example, ammonia water, and the P2-form Na is produced0.67NixMgyMn1-x-yO2In the method of (1), the alkaline solution condition may be formed by using ammonia water in the step 1).
Preferably, the sodium source is at least one of sodium hydroxide, sodium chloride, sodium nitrate and sodium acetate.
Preferably, the manganese source is at least one of manganese nitrate, manganese chloride and manganese acetate.
Preferably, the nickel source is at least one of nickel nitrate, nickel chloride and nickel acetate.
Preferably, the magnesium source is at least one of magnesium nitrate, magnesium chloride and magnesium acetate.
Preferably, the sodium source, the manganese source, the nickel source and the magnesium source are used according to the molar ratio of the P2-type Na0.67NixMgyMn1-x-yO2The metering relationship of (2) is determined.
The third solution can be heated at 40-100 ℃ to form gel.
Preferably, the P2-form Na is prepared0.67NixMgyMn1-x-yO2In the step 4), the drying conditions include: the temperature is 80-160 ℃, and the time is 6-48 h.
Preferably, the P2-form Na is prepared0.67NixMgyMn1-x-yO2In the step 4), the roasting conditions include: the temperature is 700-1200 ℃, and the time is 4-36 h. The firing may be performed under an air atmosphere.
Preferably, the positive electrode slurry forming the positive electrode further contains acetylene black and polyvinylidene fluoride.
Preferably, in the positive electrode slurry, the P2-form Na is present0.67NixMgyMn1-x-yO2And the acetylene black and the polyvinylidene fluoride are in a content weight ratio of (10-30): (1.2-3): 1.
preferably, the thickness of the solid electrolyte is 100nm to 50 μm, more preferably 500nm to 5 μm. That is, the solid electrolyte of the present invention may be in the form of a film or a sheet.
Preferably, the cathode is metallic sodium and/or a carbon material.
In a fifth aspect, the present invention provides a friction nanogenerator system comprising a friction nanogenerator and the all-solid-state sodium-ion battery of the fourth aspect, wherein the electric energy generated by the friction nanogenerator is stored in the all-solid-state sodium-ion battery.
The friction nano generator system containing the all-solid-state sodium ion battery can store electric energy generated by the friction nano generator and can realize high-efficiency and stable electric energy output.
The invention has no special limitation on the method and the structure for forming the friction nano generator, the existing friction nano generator can be used, and the invention mainly aims to provide the perfluorinated sodium polymer electrolyte and the all-solid-state sodium ion battery containing the perfluorinated sodium polymer electrolyte. The all-solid-state battery containing the sodium perfluoropolymer electrolyte of the present invention can be used by those skilled in the art to efficiently store energy captured by a triboelectric nanogenerator.
The present invention will be described in detail below by way of examples.
In the following examples, various raw materials used are commercially available without specific description.
Preparation example 1: preparation of P2-form Na0.67Ni0.23Mg0.1Mn0.67O2
The molar ratio of ethylenediaminetetraacetic acid (EDTA), citric acid and total metal ions is 1: 1.5: 1. dissolving stoichiometric amount of EDTA in NH3·H2O, and heating and stirring at 40 ℃, and then adding a calculated amount of NaNO3Adding into the above solution. When NaNO is present3After complete dissolution, the calculated amount of Mn (NO)3)2·4H2O、Ni(NO3)2·6H2O and Mg (NO)3)2·6H2O is dissolved in the above solution. After heating and stirring for 10min, the calculated amount of citric acid was added and the citric acid addition process was controlled (using NH)3·H2O adjustment) was about 6. The solution was then stirred at 70 ℃ until a gel formed and dried at 120 ℃ for 24 h. And finally, roasting the obtained precursor in the air at 900 ℃ for 15h to obtain a final product. And (5) standby.
Preparation example 2: preparation of P2-form Na0.67Ni0.42Mg0.2Mn0.38O2
This production example was conducted in a similar manner to production example 1 except that Mn (NO) in this production example3)2·4H2O、Ni(NO3)2·6H2O and Mg (NO)3)2·6H2The amount of O used was different from that in preparation example 1, but P2-form Na according to this preparation example0.67Ni0.42Mg0.2Mn0.38O2The foregoing materials were added in metered relation. The rest is the same as in preparation example 1.
Obtaining P2-type Na0.67Ni0.42Mg0.2Mn0.38O2And (5) standby.
Example 1: preparation of PFSA-Na-1
The perfluorosulfonic acid resin (PFSA) was converted to PFSA-Na-1 by ion exchange in 1M aqueous NaOH at 80 ℃ for 12 h. Then, it was washed with deionized water and dried in a glove box Ar atmosphere at 25 ℃.
The flexible PFSA-Na-1 membrane prepared in this example is shown in FIGS. 1 (a) and (b), wherein (a) is a PFSA-Na-1 membrane in a folded state; (b) is a PFSA-Na-1 membrane in a recovered state.
The PFSA-Na-1 film prepared in this example was tested for stress-strain relationship by the plastic film tensile property test method (GBT13022-1991), and a typical stress-strain relationship curve of the PFSA-Na-1 film shown in (c) of FIG. 1 was obtained.
The PFSA-Na-1 film was then soaked in 60mL of an EC-PC (v: v ═ 1: 1) mixed solvent, which was contained in a single container containing 20 g
Storing the active molecular sieve in a closed container at 25 ℃ for 48 h.
FIG. 1 (d) is an Arrhenius curve of a PFSA-Na-1 membrane swollen in an EC-PC mixed solvent.
Example 2: preparation of PFSA-Na-2
The perfluorosulfonic acid resin (PFSA) was converted to PFSA-Na-2 by ion exchange in 1M aqueous NaOH at 60 ℃ for 18 h. Then, it was washed with deionized water and dried in a glove box Ar atmosphere at 30 ℃.
The PFSA-Na-2 membrane prepared in this example was similar to the flexible PFSA-Na-1 membrane and had a typical stress-strain relationship curve similar to the flexible PFSA-Na-1 membrane.
The PFSA-Na-2 membrane was then soaked in 60mL of an EC-PC (v: v ═ 1: 1.2) mixed solvent, which was contained in a single container containing 20 g
Storing the active molecular sieve in a closed container at 30 ℃ for 40 h.
The Arrhenius curve of the swollen PFSA-Na-2 membrane obtained in this example was similar to that of the swollen PFSA-Na-1 membrane in example 1.
Preparation example 3: preparation of symmetrical Na | PFSA-Na | Na all-solid-state battery
The symmetric Na PFSA-Na cells were assembled with button cells (R2032) in an argon filled glove box.
The positive electrode slurry of the all-solid-state battery is composed of 85% of P2-type Na by mass ratio0.67Ni0.23Mg0.1Mn0.67O2(obtained in preparation example 1), 10% acetylene black and 5%Mixing polyvinylidene fluoride (PVDF), coating the positive electrode slurry on Al foil, drying at 120 ℃ in vacuum for 12 hours, cutting into electrode plates, and weighing for later use. The negative electrode of the all-solid battery was a metallic sodium foil, and the electrolyte in the symmetric Na | PFSA-Na | Na all-solid battery of this preparation example was the swollen PFSA-Na-1 film prepared in example 1.
The battery prepared in the preparation example was charged at 0.2mA/cm2The current density of (a) was subjected to a constant current charge and discharge test on a battery tester (LANDCT2001A) to determine the transference number of sodium ions. Fig. 2 (a) shows a graph of current versus time after applying a dc voltage of 5 mv for the symmetrical Na | PFSA-Na | Na cell of the present preparation example. Fig. 2 (b) shows a schematic diagram of the Na | PFSA-Na | Na battery plating/stripping experiment for the symmetric Na | PFSA-Na | Na battery of the present preparation example. (c) in FIG. 2 shows that the electric current is at 0.2mA/cm2Voltage versus time curves during the sodium plating/stripping experiments for the symmetric Na | PFSA-Na | Na cells of this preparation at current density.
Fig. 3 (a) shows the charge and discharge curves of the all-solid battery of the present preparation example at different current densities, from 5mA/g to 384 mA/g; fig. 3 (b) shows the rate performance of the all-solid battery of the present production example; fig. 3 (c) shows the long-term cycle performance, capacity and coulombic efficiency of the all-solid-state battery of the present preparation example at a current density of 5mA/g as a function of the number of cycles; fig. 3 (d) shows the long-term cycle performance, capacity and coulombic efficiency of the all-solid-state battery of this preparation example at a current density of 48mA/g as a function of the number of cycles.
Preparation example 4: preparation of symmetrical Na | PFSA-Na | Na all-solid-state battery
This preparation was carried out in a similar manner to preparation 3, except that:
the positive electrode slurry of the all-solid-state battery of the preparation example consists of 80 mass percent of P2-type Na0.67Ni0.42Mg0.2Mn0.38O2Prepared by mixing 12% acetylene black and 8% polyvinylidene fluoride (PVDF), coated on Al foil, dried at 120 ℃ in vacuum for 12 hours, cut into electrode sheets, and weighed for use. The cathode of the all-solid-state battery is metal sodiumThe foil, the electrolyte in the symmetric Na | PFSA-Na | Na cell of this preparation example, was the swollen PFSA-Na-2 film prepared in example 2.
The battery prepared in the preparation example was charged at 0.2mA/cm2The current density of (a) was subjected to a constant current charge and discharge test on a battery tester (LANDCT2001A) to determine the transference number of sodium ions. The graph of the current change with time after applying a dc voltage of 5 mv to the symmetric Na PFSA-Na cell of this preparation example is similar to that of (a) of fig. 2. The symmetrical Na | PFSA-Na | Na battery of this preparation example was at 0.2mA/cm2The voltage versus time curve during the sodium plating/stripping experiment at current density was similar to (c) in fig. 2.
The charge and discharge curves of the all-solid battery of this preparation example were similar to those of (a) in fig. 3 at different current densities (from 5mA/g to 384 mA/g); the rate performance of the all-solid battery of the present preparation example is similar to the result shown in (b) of fig. 3; the long-term cycle performance, capacity and coulombic efficiency of the all-solid-state battery of this preparation example at a current density of 5mA/g was similar to (c) in fig. 3; the long-term cycle performance, capacity and coulombic efficiency of the all-solid-state battery of this preparation example at a current density of 48mA/g were similar to those of (d) in fig. 3.
Preparation example 5: forming triboelectric nanogenerator systems
The following documents are adopted: the method provided by Zhu, g., Chen, j., Zhang, t.j., king, q.s., Wang, z.l.radial-array electrical selection for high performance triboelectric generator, nat.commun.2014,5,3426, forms a triboelectric nanogenerator, and the energy storage device of the triboelectric nanogenerator system of the present preparation example is the symmetrical Na | PFSA-Na | Na all-solid-state battery prepared in preparation example 3.
The performance of the triboelectric nanogenerator system was tested for open circuit voltage and short circuit current by connecting an electrometer in series (Keithley 6514) and a high output impedance electrometer in parallel (Keithley 6517), respectively.
Fig. 4 (a) is a schematic view of an apparatus for storing pulse energy collected by the friction nanogenerator system of this preparation example using the all-solid-state battery of preparation example 3; fig. 4 (b) is a partially enlarged view of the friction nanogenerator system of the present preparation example; fig. 4 (c) is a graph of open circuit voltage versus time for the triboelectric nanogenerator system; fig. 4 (d) is a graph of short-circuit current of the triboelectric nanogenerator system as a function of time; fig. 4 (e) is a discharge curve of the battery at different current densities after the all-solid-state battery of preparation example 3 was charged with the friction nanogenerator system of this preparation example.
Preparation example 6: forming triboelectric nanogenerator systems
The preparation example was carried out in a similar manner to preparation example 5, except that the energy storage device of the triboelectric nanogenerator system in the preparation example was the symmetrical Na | PFSA-Na | Na all-solid-state battery prepared in preparation example 4.
The open circuit voltage variation with time of the friction nanogenerator system of the present preparation example is similar to that of (c) of fig. 4; the change curve of the short-circuit current with time of the friction nano-generator system of the preparation example is similar to (d) in fig. 4; the discharge curves of the battery after charging the all-solid-state battery of preparation example 4 with the tribo nanogenerator system prepared in this preparation example at different current densities were similar to (e) in fig. 4.
From the above results of the present invention, it can be seen that: the all-solid-state sodium ion battery prepared by the scheme of the invention can be directly combined with a friction nano generator with pulse output characteristics, and the energy captured by a friction nano generator system can be efficiently stored. Compared with the existing sodium ion battery using liquid, the all-solid-state sodium ion battery prepared by the scheme of the invention has better safety and cycle performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A friction nanogenerator system comprises an all-solid-state sodium ion battery and a friction nanogenerator, wherein electric energy generated by the friction nanogenerator is stored in the all-solid-state sodium ion battery;
the all-solid-state sodium ion battery includes:
the anode is provided with a positive electrode and a negative electrode,
the solid electrolyte is a perfluorinated sodium polymer, and the thickness of the solid electrolyte is 500 nm-5 microns; and
a negative electrode;
wherein the positive electrode slurry for forming the positive electrode contains P2-type Na0.67NixMgyMn1-x-yO2(x is more than or equal to 0.23 and less than or equal to 0.5, y is more than or equal to 0.1 and less than or equal to 0.2), acetylene black and polyvinylidene fluoride;
in the positive electrode slurry, the P2-type Na0.67NixMgyMn1-x-yO2And the acetylene black and the polyvinylidene fluoride are in a content weight ratio of (10-30): (1.2-3): 1.
2. the triboelectric nanogenerator system of claim 1, a method of making the perfluorosodium polymer electrolyte comprising: mixing the perfluorinated sulfonic acid resin with Na+The solution of (a) is subjected to ion exchange.
3. The triboelectric nanogenerator system of claim 2, wherein the conditions of the ion exchange comprise: the temperature is 40-100 ℃, and the time is 6-24 h.
4. The triboelectric nanogenerator system of claim 2 or 3, wherein the method further comprises: and washing and drying the product obtained after ion exchange in sequence.
5. The triboelectric nanogenerator system of claim 4, the conditions of drying comprising: in the presence of protective gas, the temperature is 5-45 ℃ and the time is 5 minutes to 1 hour.
6. The triboelectric nanogenerator system of claim 4, wherein the method further comprises: after the drying, the dried sodium perfluoropolymer electrolyte is mixed with a mixed solvent containing ethylene carbonate and polycarbonate in the presence of a molecular sieve.
7. The triboelectric nanogenerator system of claim 6, the conditions of mixing comprising: the temperature is 5-45 ℃, and the time is 12-72 h.
8. The triboelectric nanogenerator system of claim 1, wherein the negative electrode is sodium metal and/or a carbon material.
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