WO2023024569A1 - 一种等离子体改性钠超离子导体型固态电解质的方法 - Google Patents

一种等离子体改性钠超离子导体型固态电解质的方法 Download PDF

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WO2023024569A1
WO2023024569A1 PCT/CN2022/091285 CN2022091285W WO2023024569A1 WO 2023024569 A1 WO2023024569 A1 WO 2023024569A1 CN 2022091285 W CN2022091285 W CN 2022091285W WO 2023024569 A1 WO2023024569 A1 WO 2023024569A1
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solid electrolyte
superionic conductor
sodium superionic
preset
electrolyte particles
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PCT/CN2022/091285
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English (en)
French (fr)
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梁风
侯敏杰
张涛
石祥刚
杨斌
向孙祖
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昆明理工大学
江苏风驰碳基新材料研究院有限公司
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Priority to JP2022564232A priority Critical patent/JP7480968B2/ja
Priority to US17/993,893 priority patent/US11817552B2/en
Publication of WO2023024569A1 publication Critical patent/WO2023024569A1/zh

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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of new energy materials, in particular to a method for plasma modification of a sodium superionic conductor solid state electrolyte.
  • Solid-state sodium-ion batteries are called "green energy for the 21st century". Compared with traditional lithium batteries, solid-state sodium-ion batteries have the advantages of abundant raw material reserves, low production costs, high safety performance, wide operating temperature range, and environmental friendliness. . The large-scale application of solid-state sodium-ion batteries can meet the corresponding needs of the new power system and become one of the key supports for "carbon peaking and carbon neutrality" in the energy field.
  • sodium metal anodes have been regarded as key anode materials for next-generation high-energy-density solid-state sodium-ion batteries due to their high mass specific capacity and low electrochemical potential.
  • sodium metal when sodium metal is used as the negative electrode, the growth of sodium dendrites will pierce the separator and cause internal short circuit of the battery, causing problems such as thermal runaway, flammability and explosion.
  • the use of solid electrolytes is expected to fundamentally solve the safety problems brought by organic electrolytes. question.
  • solid electrolytes have the following advantages: 1) high safety, avoiding leakage and flammability problems, and reducing the packaging requirements of battery packs; 2) expandable electrochemical window; 3) high energy density. Therefore, the development of solid-state sodium-ion batteries not only has broad application prospects, which is enough to cause revolutionary changes in energy storage devices and applications, but also plays a very important role in national energy security strategies. According to the type of solid electrolyte used, solid-state sodium-ion batteries can be mainly divided into inorganic solid-state electrolyte batteries and polymer batteries. At present, the development of solid-state sodium-ion batteries with superior performance still faces many scientific and technical challenges.
  • composite solid electrolyte has unique advantages such as small interface impedance, long cycle life, no memory function, light weight, flexibility and easy processing, which is the key to realize the miniaturization and portability of batteries.
  • problems such as low room temperature ionic conductivity, poor film-forming mechanical properties, high porosity, narrow electrochemical window, and poor interface compatibility with electrodes limit their application in solid-state sodium-ion batteries.
  • Enhancing the surface energy of inorganic solid electrolyte particles, improving their interface affinity with polymers, and obtaining composite solid electrolytes with uniform texture, low porosity, and high ionic conductivity are key issues to be solved in the development of high-performance all-solid-state sodium-ion batteries.
  • the object of the present invention is to provide a method for plasma modification of sodium superionic conductor solid electrolyte, improve the surface energy of sodium superionic conductor solid electrolyte particles, enhance the interface affinity between it and polymers, and obtain low porosity , safe, reliable, low-cost and low-cost composite solid-state electrolyte, and then optimize the cycle life and electrochemical performance of solid-state sodium-ion batteries using the above-mentioned composite solid-state electrolyte.
  • a method for plasma modification of a sodium superionic conductor type solid electrolyte includes the following steps:
  • Plasma modification treatment plasma modification treatment is performed on the sodium superionic conductor type solid electrolyte particles to obtain activated sodium superionic conductor type solid electrolyte particles;
  • Preparation of composite solid electrolyte Weigh the polymer and the activated sodium superionic conductor solid electrolyte particles according to a predetermined ratio, dissolve the polymer and the activated sodium superionic conductor solid electrolyte particles in an organic solvent to Mix the solution, then pour the mixed solution into a preset mold, and then perform vacuum drying to remove the organic solvent and form a composite solid electrolyte membrane, take out the composite solid electrolyte membrane from the preset mold and perform rolling to obtain a composite solid electrolyte membrane after rolling.
  • the plasma modification treatment is used to perform plasma activation treatment on the sodium superionic conductor solid electrolyte particles, so that the sodium The surface energy of the superionic conductor type solid electrolyte particles is increased, and the affinity with the polymer is improved.
  • the porosity of the prepared composite solid electrolyte is reduced, the ionic conductivity is increased, and the particle agglomeration phenomenon of the sodium superionic conductor type solid electrolyte is improved.
  • the above-mentioned plasma-modified sodium superionic conductor type solid electrolyte particles and the composite solid electrolyte have a simple process flow, basically do not involve complex reaction processes, and reduce energy consumption and equipment investment.
  • basically no "three wastes" are generated in any process link of the present invention, which conforms to the concept of green industry and is friendly to the environment.
  • the plasma activation treatment adopts a preset plasma atmosphere, a preset gas flow rate, a preset Voltage, preset current and first preset time
  • the preset plasma atmosphere is one of nitrogen, oxygen, argon, nitrogen-oxygen mixed gas, nitrogen-argon mixed gas, and air
  • the preset plasma atmosphere The pressure is atmospheric pressure
  • the preset voltage is the voltage applied to the sodium superionic conductor type solid electrolyte particles and the voltage range is 10V to 150V
  • the preset current is applied to the sodium superionic conductor type solid electrolyte particles
  • the current range is 0.2A-2A
  • the first preset time is 1min-60min.
  • the plasma activation treatment adopts the above preset plasma atmosphere, preset gas flow rate, preset voltage, preset current and first preset time, which can make the sodium superionic conductor solid electrolyte have a high Surface energy and excellent affinity to polymer interfaces.
  • the preset ratio is the mass ratio of the polymer to the activated sodium superionic conductor type solid electrolyte particles, and the mass ratio ranges from 10wt.% to 80wt.%.
  • the porosity can be reduced, polymer crystallization can be effectively suppressed, the glass transition temperature can be lowered, and better mechanical and ionic conductivity can be exhibited.
  • the conductivity is high, and the battery has excellent cycle performance.
  • the polymeric species includes polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol ( PEG) at least one.
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF-HFP poly(vinylidene fluoride-co-hexafluoropropylene)
  • PEG polyethylene glycol
  • the organic solvent includes one or two of acetone, N,N-dimethylformamide (DMF), acetonitrile, and N-methylpyrrolidone (NMP).
  • DMF N,N-dimethylformamide
  • NMP N-methylpyrrolidone
  • the polymer and the activated sodium superionic conductor solid electrolyte particles in the organic solvent to obtain a mixed solution
  • the conductive solid electrolyte particles are dissolved in the organic solvent and subjected to mechanical ball milling to obtain the mixed solution.
  • the mechanical ball milling is carried out at a predetermined mechanical ball milling speed, the predetermined mechanical ball milling speed range may be 150r/min-400r/min, the time of the mechanical ball milling is a second preset time, and the second predetermined It is assumed that the range of the time may be 5h-48h.
  • the mechanical ball milling at the above speed and time can make the polymer and the activated sodium superionic conductor type solid electrolyte particles dissolve in the organic solvent more uniformly, reduce the generation of bubbles, and further refine the sodium superionic conductor solid electrolyte particles.
  • the crystal grains of ion conductor type solid electrolyte particles can make the composite solid electrolyte have smaller impedance, longer cycle performance, and more excellent electrochemical performance.
  • the step of pouring the mixed solution into a preset mold and drying to remove the organic solvent and form a composite solid electrolyte membrane includes: pouring the mixed solution into the preset mold Set the mold in a vacuum drying oven, then adjust the temperature in the vacuum drying oven to a preset temperature and keep it for a third preset time to obtain the composite solid electrolyte membrane; the third preset time
  • the range is 15h-48h; the range of the preset temperature is 40°C-100°C.
  • the plasma modification treatment is used to perform plasma activation treatment on the sodium superionic conductor type solid electrolyte particles, and cast them into a film, so that
  • the sodium superionic conductor type composite solid electrolyte membrane increases the solid-solid interface compatibility, reduces the interface impedance, reduces the polarization of the battery, and can prolong the cycle life of the solid-state battery using the composite solid electrolyte membrane, and has superior performance.
  • adopting the third predetermined time and the above-mentioned preset temperature range can also make the finally activated composite solid electrolyte membrane have better microstructure and mechanical properties.
  • the thickness of the composite solid electrolyte membrane after the rolling treatment is 30 ⁇ m to 100 ⁇ m, which can make the performance of the activated composite solid electrolyte membrane better, such as having better sodium ion transport performance , The advantages of better battery cycle performance.
  • the method for preparing the plasma-modified sodium superionic conductor type solid electrolyte particles and the composite solid electrolyte has a simple process flow, basically does not involve complex reaction processes, and reduces energy consumption and investment in equipment.
  • basically no "three wastes" are generated in any process link of the present invention, which conforms to the concept of green industry and is friendly to the environment.
  • Fig. 1 is a schematic diagram of the method steps of a plasma-modified sodium superionic conductor type solid electrolyte particle provided by the present invention
  • Fig. 2 is the method step schematic diagram of another kind of plasma modification sodium superionic conductor type solid electrolyte particle provided by the present invention.
  • Fig. 3 is the scanning electron micrograph (SEM) of the composite solid electrolyte prepared by the unmodified sodium superionic conductor type solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 4 is the scanning electron micrograph (SEM) of the composite solid electrolyte prepared by plasma-modified sodium superionic conductor type solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 5 is the X-ray diffraction pattern (XRD) of the plasma modified/unmodified sodium superionic conductor type solid electrolyte particle that the first implementation of the present invention obtains;
  • Fig. 6 is the energy spectrum analysis (EDS) of the composite solid electrolyte prepared by the unmodified sodium superionic conductor type solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 7 is the energy spectrum analysis (EDS) of the composite solid electrolyte prepared by plasma-modified sodium superionic conductor type solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 8 is a symmetric battery (Na/composite solid electrolyte/Na) cycle comparison diagram for preparing a composite solid electrolyte from plasma modified/unmodified sodium superionic conductor solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 9 is the electrochemical impedance spectroscopy (EIS) comparison diagram of the composite solid electrolyte prepared by plasma modified/unmodified treated sodium superionic conductor type solid electrolyte particles obtained by the first implementation of the present invention
  • Fig. 10 is a symmetric battery (Na/composite solid electrolyte/Na) cycle diagram for preparing a composite solid electrolyte from plasma-modified sodium superionic conductor solid electrolyte particles obtained in the second implementation of the present invention
  • Fig. 11 is the electrochemical impedance spectroscopy (EIS) of the composite solid electrolyte prepared by plasma-modified sodium superionic conductor solid electrolyte particles obtained in the third implementation of the present invention.
  • EIS electrochemical impedance spectroscopy
  • the molecular formula of the sodium superionic conductor solid electrolyte of the sodium superionic conductor (NASICON) solid electrolyte particles involved in the embodiment of the present invention is Na x Zr 2 Six -1 P 4-x O 12 , wherein, 1 ⁇ x ⁇ 4 .
  • the embodiment of the present invention utilizes the plasma modification function to effectively improve the surface energy of the sodium superionic conductor solid electrolyte particles, and improve the interface affinity between the sodium superionic conductor solid electrolyte particles and the polymer.
  • the porosity of the electrolyte membrane is reduced, and the sodium superionic conductor type solid electrolyte particles are evenly distributed, which promotes the uniform deposition of lithium metal, and improves the stability and cycle life of the solid-state sodium-ion battery.
  • the method for plasma modification of sodium superionic conductor type solid electrolyte particles comprises the following steps:
  • Plasma modification treatment plasma modification treatment is performed on the sodium superionic conductor type solid electrolyte particles to obtain activated sodium superionic conductor type solid electrolyte particles;
  • Preparation of composite solid electrolyte Weigh the polymer and the activated sodium superionic conductor solid electrolyte particles according to a predetermined ratio, and dissolve the polymer and the activated sodium superionic conductor solid electrolyte particles in an organic solvent to obtain Mix the solution, then pour the mixed solution into a preset mold, and then perform vacuum drying to remove the organic solvent and form a composite solid electrolyte membrane, take out the composite solid electrolyte membrane from the preset mold and perform rolling to obtain a composite solid electrolyte membrane after rolling.
  • the plasma modification treatment is used to perform plasma activation treatment on the sodium superionic conductor solid electrolyte particles, so that the sodium
  • the porosity of the composite solid electrolyte prepared by superionic conductor solid electrolyte particles is reduced, the growth of lithium dendrites is inhibited, the interfacial impedance is reduced, the polarization of the battery is reduced, and the use of the above plasma-modified sodium superionic conductor solid electrolyte particles is prolonged.
  • the cycle life of the solid-state battery of the composite solid electrolyte is excellent, and the electrochemical performance is superior.
  • the above-mentioned method and application process of the plasma-modified sodium superionic conductor solid electrolyte are simple, basically do not involve complex reaction processes, and reduce energy consumption and investment in equipment.
  • basically no "three wastes" are generated in any process link of the present invention, which conforms to the concept of green industry and is friendly to the environment.
  • the step of performing plasma modification treatment on the sodium superionic conductor type solid electrolyte particles includes: plasma modification treatment on the sodium superionic conductor type solid electrolyte particles, and the plasma modification treatment adopts a preset plasma Plasma atmosphere, preset gas flow rate, preset voltage, preset current and first preset time, the preset plasma atmosphere is nitrogen, oxygen, argon, nitrogen-oxygen mixed gas, nitrogen-argon mixed gas, in the air
  • the pressure of the preset plasma atmosphere is atmospheric pressure
  • the preset voltage is the voltage applied to the sodium superionic conductor type solid electrolyte particles and the voltage range is 10V-150V
  • the preset current is applied at The current range of the sodium superionic conductor type solid electrolyte particles is 0.2A-2A
  • the first preset time is 1min-60min.
  • the plasma activation treatment adopts the above preset plasma atmosphere, preset gas flow rate, preset voltage, preset current and first preset time, which can make the composite solid electrolyte have an excellent microscopic crystal structure , porosity, ionic conductivity and battery cycle performance.
  • the preset ratio is the mass ratio of the polymer to the activated sodium superionic conductor type solid electrolyte particles, and the mass ratio ranges from 10wt.% to 80wt.%.
  • the porosity can be effectively reduced, polymer crystallization can be suppressed, and the glass transition temperature can be lowered.
  • the mechanical properties and ionic conductivity of the finally obtained sodium superionic conductor type composite solid electrolyte membrane are relatively high, And the battery has better cycle performance.
  • the polymeric species includes polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol ( PEG) at least one.
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF-HFP poly(vinylidene fluoride-co-hexafluoropropylene)
  • PEG polyethylene glycol
  • the organic solvent includes one or two of acetone, N,N-dimethylformamide (DMF), acetonitrile, and N-methylpyrrolidone (NMP).
  • DMF N,N-dimethylformamide
  • NMP N-methylpyrrolidone
  • the polymer and the activated sodium superionic conductor type solid electrolyte particles are dissolved in the organic solvent for mechanical ball milling at the predetermined mechanical ball milling speed, and the predetermined mechanical ball milling speed range is 150r /min ⁇ 400r/min.
  • the predetermined mechanical ball milling speed range is 150r /min ⁇ 400r/min.
  • using the above-mentioned mechanical ball milling speed can make the polymer and the activated sodium superionic conductor type solid electrolyte particles dissolve more uniformly in the organic solvent mixture, reduce the generation of bubbles, and further refine the sodium superionic particles.
  • the crystal grains of conductive solid electrolyte particles can make the composite solid electrolyte have smaller impedance, longer cycle performance, and more excellent electrochemical performance.
  • the composite solid electrolyte membrane is obtained by using the activated sodium superionic conductor solid electrolyte particles.
  • the step of performing plasma activation treatment on the sodium superionic conductor type solid electrolyte particles to obtain activated sodium superionic conductor type solid electrolyte particles may include the specific steps of the plasma modification treatment shown in Figure 1 above.
  • the step of using the activated sodium superionic conductor type solid electrolyte particles to obtain a composite solid electrolyte membrane may include the preparation steps of the composite solid electrolyte shown in FIG. 1 above, which will not be described here.
  • the thickness of the composite solid electrolyte membrane may be 30 ⁇ m to 100 ⁇ m; it can be understood that in the above-mentioned method for plasma modification of sodium superion conductor solid electrolyte particles, plasma modification treatment is used to treat the sodium superion conductor Body-shaped solid electrolyte particles are subjected to plasma activation treatment, and cast into a film, so that the sodium superionic conductor type composite solid electrolyte film increases solid-solid interface compatibility, reduces interface impedance, reduces battery polarization, and can be used for a long time The cycle life of the solid-state battery of the above-mentioned composite solid-state electrolyte membrane is excellent, and the performance is superior.
  • the thickness of the composite solid electrolyte membrane is 30 ⁇ m to 100 ⁇ m, which can make the performance of the activated composite solid electrolyte membrane better, for example, it has the advantages of better sodium ion transport performance and better battery cycle performance.
  • the method for preparing the plasma-modified sodium superionic conductor type solid electrolyte particles and the composite solid electrolyte has a simple process flow, basically does not involve complex reaction processes, and reduces energy consumption and investment in equipment. In addition, basically no "three wastes" are generated in any process link of the present invention, which conforms to the concept of green industry and is friendly to the environment.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 5 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 1A, and the voltage is 100V, and then cooled to At room temperature, activated sodium superionic conductor type solid electrolyte particles are obtained;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 20wt.%, and combine PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 250r/min for 24 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness 20 ⁇ m, placed in a vacuum drying oven at 80°C for 24 hours to remove the above organic solvent, to obtain a composite solid electrolyte membrane.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 1 min under nitrogen conditions, the gas flow rate is 10m/s, the working current is 2A, and the voltage is 150V, and then cooled to At room temperature, activated sodium superionic conductor type solid electrolyte particles are obtained;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 80wt.%, and combine PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 400r/min for 5h, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness 100 ⁇ m, put it into a vacuum oven at 80°C and let it stand for 15 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • the symmetric battery (Na/composite solid electrolyte/Na) of a composite solid electrolyte with an activated sodium superionic conductor type solid electrolyte particle content of 80wt.% can be stably cycled for more than 2100h, and has a stable voltage of 0.5V. Polarization voltage.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 60 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 0.2A, and the voltage is 10V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 10wt.%, and combine PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 150r/min for 48 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness of 30 ⁇ m, put it into a vacuum oven at 40°C and let it stand for 48 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • the AC impedance test is carried out on the composite solid electrolyte, as shown in Figure 11, the composite solid electrolyte prepared based on the activated sodium superionic conductor solid electrolyte particles has a significant impedance reduction compared with the unmodified composite solid electrolyte Advantage, the interface impedance is reduced from 58 ⁇ to 47 ⁇ .
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 5 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 1.5A, and the voltage is 130V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 20wt.%, and combine PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 250r/min for 24 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness 40 ⁇ m, put it into a vacuum oven at 40°C and let it stand for 48 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 10 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 1.5A, and the voltage is 130V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 50wt.%, and mix PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 350r/min for 10 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness 50 ⁇ m, put it into a vacuum oven at 40°C and let it stand for 36 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • the present embodiment carries out physical and electrochemical tests on the composite solid electrolyte, which has relatively low impedance and polarization compared with untreated ones, and longer cycle life.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 40 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 0.8A, and the voltage is 60V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 30wt.%, and combine PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N, N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 300r/min for 30 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness of 60 ⁇ m, put it into a vacuum oven at 60°C and let it stand for 36 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 50 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 1.2A, and the voltage is 80V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;
  • step (2) Preparation of composite solid electrolyte: take PVDF-HFP and the activated sodium superionic conductor type solid electrolyte particles obtained in step (1) according to the ratio of 50wt.%, and mix PVDF-HFP and activated sodium superionic conductor type solid state electrolyte
  • the electrolyte particles were dissolved in acetone and N,N-dimethylformamide, and the mixed solution was obtained by mechanical ball milling at a speed of 400r/min for 30 hours, and then the above mixed solution was slowly poured into a polytetrafluoroethylene mold, and then rolled to a thickness of 60 ⁇ m, put it into a vacuum oven at 60°C and let it stand for 36 hours to remove the above organic solvent to obtain a composite solid electrolyte membrane.
  • Plasma modification treatment the sodium superionic conductor type solid electrolyte particles are subjected to low-temperature plasma activation treatment for 60 minutes under nitrogen conditions, the gas flow rate is 10m/s, the working current is 0.5A, and the voltage is 40V, and then cooled to room temperature to obtain activated sodium superionic conductor type solid electrolyte particles;

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Abstract

本发明公开了一种等离子体改性钠超离子导体型固态电解质的方法，所述方法包括：对钠超离子导体型固态电解质颗粒进行等离子体改性处理，得到活化钠超离子导体型固态电解质颗粒；按照预订的比例称取聚合物与所述活化钠超离子导体型固态电解质颗粒，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于有机溶剂中得到混合溶液，然后将所述混合溶液浇注到预设模具中，再进行干燥以去除所述有机溶剂并成形为复合固态电解质膜，从所述预设模具中取出所述复合固态电解质膜并进行辊压，得到辊压处理后的复合固态电解质膜。本发明方法生产周期短、成本低、可大规模商业化，进一步实现固态电解质在商业化中的应用。

Description

一种等离子体改性钠超离子导体型固态电解质的方法 技术领域
本发明涉及新能源材料领域，特别涉及一种等离子体改性钠超离子导体型固态电解质的方法。
背景技术
在“双碳”国家战略目标驱动下，加快优化能源结构，构建以新能源为主体的新型电力系统已成为必然趋势。开发新型能源材料与储能器件对推动能源绿色转型、应对极端事件、保障能源安全、促进能源高质量发展、实现“双碳”目标具有重要意义。
固态钠离子电池被称为“面向21世纪的绿色能源”，相较于传统锂电池，固态钠离子电池具有原材料储量丰富、生产成本低、安全性能高、工作环境温度范围大、环境友好等优点。固态钠离子电池的规模化应用能够满足新型电力系统相应需求，成为能源领域“碳达峰，碳中和”的关键支撑之一。
近年来，由于钠金属负极具有较高的质量比容量以及低的电化学电势被视作下一代高能量密度固态钠离子电池的关键负极材料。但是，钠金属作为负极时，钠枝晶的生长会刺穿隔膜造成电池内部短路，造成热失控、易燃易爆等问题，固态电解质的使用有希望从根本上解决有机电解液带来的安全问题。
此外，固态电解质具有以下几大优点：1)高安全性，避免泄漏和可燃性问题的发生，降低电池包封装要求；2)可拓展的电化学窗口；3)高能量密度。因此，固态钠离子电池的开发不仅具有广泛的应用前景，足以引起储能器件与应用的革命性变化，且对国家能源安全战略也有非常重要的作用。根据使用固态电解质的种类，固态钠离子电池主要可以分为无机固态电解质电池和聚合物电池等。目前，开发性能优越的固态钠离子电池，仍然面临诸多科学与技术挑战。
复合固态电解质结合聚合物电解质与无机固态电解质，具有界面阻抗小、循环寿命长、无记忆功能、质轻柔韧和易加工等独特优点，是实现电池微型化和便携化的关键。然而，此类材料的室温离子电导率低、成膜力学性能差、孔隙率高、电化学窗口窄以及与电极间界面相容性差等问题限制了其在固态钠离子电池中的应用。增强无机固态电解质颗粒表面能，改善其与聚合物界 面亲和性，获得质地均匀、低孔隙率、高离子电导率的复合固态电解质，是发展高性能全固态钠离子电池需要解决的关键问题。
发明内容
本发明的目的在于提供一种等离子体改性钠超离子导体型固态电解质的方法，提高钠超离子导体型固态电解质颗粒表面能，增强其与聚合物间的界面亲和性，获得低孔隙率、安全可靠、成本低廉且界面阻抗小的复合固态电解质，进而优化使用上述复合固态电解质的固态钠离子电池循环寿命和电化学性能。
为实现上述发明目的，本发明一种实施例提供的等离子体改性钠超离子导体型固态电解质的方法包括以下步骤：
等离子体改性处理：对钠超离子导体型固态电解质颗粒进行等离子体改性处理，所得到的活化钠超离子导体型固态电解质颗粒；
复合固态电解质的制备：按照预订的比例称取聚合物与所述活化钠超离子导体型固态电解质颗粒，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于有机溶剂中到混合溶液，然后将所述混合溶液浇注到预设模具中，再进行真空干燥以去除所述有机溶剂并成形为复合固态电解质膜，从所述预设模具中取出所述复合固态电解质膜并进行辊压，得到辊压处理后的复合固态电解质膜。
相较于现有技术，上述等离子体改性钠超离子导体型固态电解质颗粒的方法中，采用等离子改性处理对所述钠超离子导体型固态电解质颗粒进行等离子体活化处理，使得所述钠超离子导体型固态电解质颗粒表面能增加，与聚合物间的亲和性得到改善。所制备的复合固态电解质孔隙率降低，离子电导率增大，钠超离子导体型固态电解质颗粒团聚现象得到改善。应用于固态钠离子电池，可减小界面阻抗、降低电池极化、抑制锂枝晶生长，并延长电池的循环寿命，提高电池包电化学性能。此外，上述等离子体改性钠超离子导体型固态电解质颗粒及复合固态电解质制备的工艺流程简单，基本不涉及复杂的反应过程，降低了能耗和设备的投资。另外，本发明的任何工艺环节基本没有“三废”的产生，符合绿色产业理念，对环境友好。
在一些实施例中，所述对所述钠超离子导体型固态电解质颗粒进行等离子体改性处理的步骤中，且所述等离子体活化处理采用预设等离子体气氛、 预设气体流速、预设电压、预设电流及第一预设时间，所述预设等离子体气氛为氮气、氧气、氩气、氮氧混合气、氮氩混合气、空气中的一种，所述预设等离子体气氛的压强为大气压，所述预设电压为施加在所述钠超离子导体型固态电解质颗粒的电压且电压范围为10V～150V，所述预设电流施加在所述钠超离子导体型固态电解质颗粒的电流且电流范围为0.2A～2A，所述第一预设时间为1min～60min。具体的，所述等离子体活化处理采用以上的预设等离子体气氛、预设气体流速、预设电压、预设电流及第一预设时间，可以使得所述钠超离子导体型固态电解质具有高表面能以及与聚合物界面间的优异亲和性。
在一些实施例中，预设比例为所述聚合物与所述活化钠超离子导体型固态电解质颗粒质量比例，所述质量比例的范围为10wt.％～80wt.％。具体地，按照上述预设比例，可以降低孔隙率，有效抑制聚合物结晶，降低玻璃化转变温度，呈现出较好的机械性和离子电导性能，最终获得的复合固态电解质膜的机械性能和离子电导率较高，且电池具有较优良的循环性能。
在一些实施例中，所述聚合物种包括聚氧化乙烯(PEO)、聚偏氟乙烯(PVDF)、聚(偏二氟乙烯-co-六氟丙烯)(PVDF-HFP)、聚乙二醇(PEG)中的至少一种。具体地，采用上述聚合物，以其电化学稳定性好、介电常数高，热力学稳定性好以及有利于离子快速迁移的结构等优势，可以使得最终获得所述复合固态电解质膜具有低孔隙率、较优的离子电导率、机械性能以及电化学性能。
在一些实施例中，所述有机溶剂包括丙酮、N,N-二甲基甲酰胺(DMF)、乙腈、N-甲基吡咯烷酮(NMP)中的一种或两种。具体地，采用上述溶剂，与上述聚合物相容性良好，最终获得的所述复合固态电解质膜具有较优的微观结构和机械性能。
在一些实施例中，所述将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于所述有机溶剂得到混合溶液的步骤中，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于所述有机溶剂并进行机械球磨得到所述混合溶液。具体地，所述机械球磨在预定机械球磨转速下进行，所述预定机械球磨转速范围可以为150r/min～400r/min，所述机械球磨的时间为第二预设时间，所述第二预设时间的范围可以为5h～48h。具体地，采用上述转速和时间的机械球磨，可以使得所述聚合物与所述活化钠超离子导体型固态 电解质颗粒溶在所述有机溶剂中更加均匀、减少气泡的产生、进一步细化钠超离子导体型固态电解质颗粒的晶粒，可以使得所述复合固态电解质具有更加小的阻抗、更长循环性能、更加优异的电化学性能。
在一些实施例中，所述将所述混合溶液浇注到预设模具中，再进行干燥以去除所述有机溶剂并成形为复合固态电解质膜的步骤包括：将所述混合溶液浇注到所述预设模具中，并放入真空干燥箱，然后将所述真空干燥箱中的温度调节至预设温度并保持第三预设时间从而得到所述复合固态电解质膜；所述第三预设时间的范围为15h～48h；所述预设温度的范围为40℃～100℃。
可以理解，上述等离子体改性钠超离子导体型固态电解质颗粒的方法中，采用等离子体改性处理对所述钠超离子导体型固态电解质颗粒进行等离子体活化处理，将其浇筑成膜，使得所述钠超离子导体型复合固态电解质膜增加固-固界面兼容性，界面阻抗降低，电池的极化降低，并且可延长使用上述复合固态电解质膜的固态电池的循环寿命，且性能优越。具体地，采用第三预定时间和上述预设温度范围，也可以使得最终得到活化后的所述复合固态电解质膜具有较优的微观结构、机械性能。
在一些实施例中，所述辊压处理后的复合固态电解质膜的厚度为30μm～100μm，可以使得所述活化后的所述复合固态电解质膜的性能较佳，如具有钠离子传输性能较佳、电池循环性能较佳的优点。
进一步地，上述等离子体改性钠超离子导体型固态电解质颗粒及复合固态电解质制备的方法工艺流程简单，基本不涉及复杂的反应过程，降低了能耗和设备的投资。另外，本发明的任何工艺环节基本没有“三废”的产生，符合绿色产业理念，对环境友好。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明提供的一种等离子体改性钠超离子导体型固态电解质颗粒的方法步骤示意图；
图2是本发明提供的另一种等离子体改性钠超离子导体型固态电解质颗 粒的方法步骤示意图；
图3是本发明第一种实施得到的未改性钠超离子导体型固态电解质颗粒制备复合固态电解质的扫描电镜图(SEM)；
图4是本发明第一种实施得到的等离子体改性钠超离子导体型固态电解质颗粒制备复合固态电解质的扫描电镜图(SEM)
图5是本发明第一种实施得到的等离子体改性/未改性钠超离子导体型固态电解质颗粒的X射线衍射图(XRD)；
图6是本发明第一种实施得到的未改性钠超离子导体型固态电解质颗粒制备复合固态电解质的能谱分析(EDS)；
图7是本发明第一种实施得到的等离子体改性钠超离子导体型固态电解质颗粒制备复合固态电解质的能谱分析(EDS)；
图8是本发明第一种实施得到的等离子体改性/未改性钠超离子导体型固态电解质颗粒制备复合固态电解质的对称电池(Na/复合固态电解质/Na)循环对比图；
图9是本发明第一种实施得到的等离子体改性/未改性处理钠超离子导体型固态电解质颗粒制备复合固态电解质的电化学阻抗谱图(EIS)对比图；
图10是本发明第二种实施得到的等离子体改性钠超离子导体型固态电解质颗粒制备复合固态电解质的对称电池(Na/复合固态电解质/Na)循环图；
图11是本发明第三种实施得到的等离子体改性钠超离子导体型固态电解质颗粒制备复合固态电解质的电化学阻抗谱图(EIS)。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
如前所述，目前开发性能优越的固态钠离子电池，仍然面临诸多科学与技术挑战：例如，较大的界面(电极/固态电解质)电阻、电极材料体积变化、电极活性材料的低负载、以及循环稳定性差等。在众多挑战之中，亟需解决的一个重要挑战是提高固态电解质密度，降低孔隙率，抑制锂金属在孔隙处的不均匀沉积，克服这一挑战的关键是能否对无机固态电解质颗粒进行表面 改性，提高无机固态电解质与有机物的界面亲和性。
本发明实施例涉及的钠超离子导体(NASICON)型固态电解质颗粒的钠超离子导体型固态电解质的分子式为Na xZr 2Si x-1P 4-xO 12，其中，1≤x≤4。本发明实施例利用等离子体改性功能有效的提高了钠超离子导体型固态电解质颗粒表面能，改善了钠超离子导体型固态电解质颗粒与聚合物间的界面亲和性，所制备的复合固态电解质膜孔隙率降低，钠超离子导体型固态电解质颗粒分布均匀，促进了锂金属的均匀沉积，提高了固态钠离子电池稳定性及循环寿命。
具体地，如图1所示，本发明提供的等离子体改性钠超离子导体型固态电解质颗粒的方法包括以下步骤：
等离子体改性处理：对钠超离子导体型固态电解质颗粒进行等离子体改性处理，所得到的活化钠超离子导体型固态电解质颗粒；
复合固态电解质的制备：按照预订的比例称取聚合物与所述活化钠超离子导体型固态电解质颗粒，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于有机溶剂中得到混合溶液，然后将所述混合溶液浇注到预设模具中，再进行真空干燥以去除所述有机溶剂并成形为复合固态电解质膜，从所述预设模具中取出所述复合固态电解质膜并进行辊压，得到辊压处理后的复合固态电解质膜。
相较于现有技术，上述等离子体改性钠超离子导体型固态电解质颗粒的方法中，采用等离子改性处理对所述钠超离子导体型固态电解质颗粒进行等离子体活化处理，使得所述钠超离子导体型固态电解质颗粒制备的复合固态电解质孔隙率降低，抑制锂枝晶生长，界面阻抗降低，电池的极化降低，并延长使用上述等离子体改性钠超离子导体型固态电解质颗粒制备的复合固态电解质的固态电池循环寿命，且电化学性能优越。此外，上述等离子体改性钠超离子导体型固态电解质的方法及应用的工艺流程简单，基本不涉及复杂的反应过程，降低了能耗和设备的投资。另外，本发明的任何工艺环节基本没有“三废”的产生，符合绿色产业理念，对环境友好。
对所述钠超离子导体型固态电解质颗粒进行等离子体改性处理的步骤包括：对所述钠超离子导体型固态电解质颗粒等离子体改性处理，且所述等离子体改性处理采用预设等离子体气氛、预设气体流速、预设电压、预设电流及第一预设时间，所述预设等离子体气氛为氮气、氧气、氩气、氮氧混合气、 氮氩混合气、空气中的一种，所述预设等离子体气氛的压强为大气压，所述预设电压为施加在所述钠超离子导体型固态电解质颗粒的电压且电压范围为10V～150V，所述预设电流施加在所述钠超离子导体型固态电解质颗粒的电流且电流范围为0.2A～2A，所述第一预设时间为1min～60min。具体的，所述等离子体活化处理采用以上的预设等离子体气氛、预设气体流速、预设电压、预设电流及第一预设时间，可以使得所述复合固态电解质具有优异的微观晶体结构、孔隙率、离子电导率以及电池循环性能。
在一些实施例中，所述预设比例为所述聚合物与所述活化钠超离子导体型固态电解质颗粒质量比例，所述质量比例的范围为10wt.％～80wt.％。具体地，按照上述预设比例，可以有效降低孔隙率、抑制聚合物结晶，降低玻璃化转变温度，最终获得的所述钠超离子导体型复合固态电解质膜的机械性能和离子电导率较高，且电池具有较优良的循环性能。
在一些实施例中，所述聚合物种包括聚氧化乙烯(PEO)、聚偏氟乙烯(PVDF)、聚(偏二氟乙烯-co-六氟丙烯)(PVDF-HFP)、聚乙二醇(PEG)中的至少一种。具体地，采用上述聚合物，以其电化学稳定性好、介电常数高，热力学稳定性好以及有利于离子快速迁移的结构等优势，可以使得最终获得的所述复合固态电解质膜具有较优的孔隙率、离子电导率、机械性能以及电化学性能。
在一些实施例中，所述有机溶剂包括丙酮、N,N-二甲基甲酰胺(DMF)、乙腈、N-甲基吡咯烷酮(NMP)中的一种或两种。具体地，采用上述溶剂，与上述聚合物相容性良好，最终获得的所述复合固态电解质膜具有较优的微观结构和机械性能。
在一些实施例中，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于所述有机溶剂在所述预定机械球磨转速下进行机械球磨，所述预定机械球磨转速范围为150r/min～400r/min。具体地，采用上述转速的机械球磨，可以使得所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶在所述有机溶剂混中更加均匀、减少气泡的产生、进一步细化钠超离子导体型固态电解质颗粒的晶粒，可以使得所述复合固态电解质具有更加小的阻抗、更长循环性能、更加优异的电化学性能。
进一步地，本发明提供的一种等离子体改性钠超离子导体型固态电解质的方法还可以简要概括如下:
对钠超离子导体型固态电解质颗粒进行等离子体活化处理，得到活化钠超离子导体型固态电解质颗粒；
利用所述活化钠超离子导体型固态电解质颗粒获取复合固态电解质膜。
其中，可以理解，对钠超离子导体型固态电解质颗粒进行等离子体活化处理，得到活化钠超离子导体型固态电解质颗粒的步骤可以包括具体采用上述图1所示的等离子体改性处理的具体步骤。所述利用所述活化钠超离子导体型固态电解质颗粒获取复合固态电解质膜的步骤可以包括上述图1所示的复合固态电解质的制备步骤，此处就不再展开及赘述。
具体地，所述复合固态电解质膜的厚度可以为30μm～100μm；可以理解，上述等离子体改性钠超离子导体型固态电解质颗粒的方法中，采用等离子体改性处理对所述钠超离子导体型固态电解质颗粒进行等离子体活化处理，将其浇筑成膜，使得所述钠超离子导体型复合固态电解质膜增加固-固界面兼容性，界面阻抗降低，电池的极化降低，并且可延长使用上述复合固态电解质膜的固态电池的循环寿命，且性能优越。此外，所述复合固态电解质膜厚度为30μm～100μm，可以使得所述活化后的所述复合固态电解质膜的性能较佳，如具有钠离子传输性能较佳、电池循环性能较佳的优点。进一步地，上述等离子体改性钠超离子导体型固态电解质颗粒及复合固态电解质制备的方法工艺流程简单,基本不涉及复杂的反应过程，降低了能耗和设备的投资。另外，本发明的任何工艺环节基本没有“三废”的产生，符合绿色产业理念，对环境友好。
以下结合第一至第八种实施例对本发明进行详细说明。
第一种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为1A，电压为100V，进行低温等离子体活化处理5min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照20wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为250r/min机械球磨24h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为20μm，放入温度为80℃的真空 干燥箱静置24h以去除上述有机溶剂，得到复合固态电解质膜。
本实例对等离子体活化处理得到的PVDF-HFP基钠超离子导体型复合固态电解质进行物理及电化学测试，对比图3和图4的扫描电镜可以得出，与未处理相比，进行低温等离子体活化处理过后其表面裂纹减少，孔隙率降低。由图5可得处理前后衍射峰位置和强度没有明显变化，证实等离子体活化处理并未改变钠超离子导体晶体结构。对比图6与图7可知，经过低温等离子体活化处理过后其粒径尺寸和元素分布更加均匀，团聚明显减少。由图8和图9可得，与未处理相比较，电池的极化从0.85V降到0.55V，可稳定循环1800h以上，界面阻抗从58Ω降低到24Ω。
第二种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为2A，电压为150V，进行低温等离子体活化处理1min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照80wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为400r/min机械球磨5h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为100μm，放入温度为80℃的真空干燥箱静置15h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例如图10所示，活化钠超离子导体型固态电解质颗粒含量为80wt.％的复合固态电解质的对称电池(Na/复合固态电解质/Na)可稳定循环2100h以上，且具有0.5V的稳定极化电压。
第三种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为0.2A，电压为10V，进行低温等离子体活化处理60min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照10wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过 转速为150r/min机械球磨48h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为30μm，放入温度为40℃的真空干燥箱静置48h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行交流阻抗测试，如图11所示，基于活化钠超离子导体型固态电解质颗粒制备的复合固态电解质与未改性复合固态电解质相比，具有明显的阻抗降低优势，界面阻抗从58Ω降低到47Ω。
第四种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为1.5A，电压为130V，进行低温等离子体活化处理5min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照20wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为250r/min机械球磨24h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为40μm，放入温度为40℃的真空干燥箱静置48h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行物理及电化学测试，与未处理的相比具有相对较低阻抗和极化，以及较长的循环寿命。
第五种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为1.5A，电压为130V，进行低温等离子体活化处理10min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照50wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为350r/min机械球磨10h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为50μm，放入温度为40℃的真空干燥箱静置36h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行物理及电化学测试，与未处理的相 比具有相对较低阻抗和极化，以及较长的循环寿命。
第六种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为0.8A，电压为60V，进行低温等离子体活化处理40min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照30wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为300r/min机械球磨30h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为60μm，放入温度为60℃的真空干燥箱静置36h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行物理及电化学测试，与未处理的相比具有相对较低阻抗和极化，以及较长的循环寿命。
第七种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为1.2A，电压为80V，进行低温等离子体活化处理50min，然后冷却到室温，得到活化钠超离子导体型固态电解质颗粒；
(2)复合固态电解质的制备：按照50wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为400r/min机械球磨30h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为60μm，放入温度为60℃的真空干燥箱静置36h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行物理及电化学测试，与未处理的相比具有相对较低阻抗和极化，以及较长的循环寿命。
第八种实施例
(1)等离子体改性处理：将钠超离子导体型固态电解质颗粒在氮气条件下，气体流速为10m/s，工作电流为0.5A，电压为40V，进行低温等离子体活化处理60min，然后冷却到室温，得到活化钠超离子导体型固态电解质 颗粒；
(2)复合固态电解质的制备：按照50wt.％的比例称取PVDF-HFP与步骤(1)中得到的活化钠超离子导体型固态电解质颗粒，将PVDF-HFP与活化钠超离子导体型固态电解质颗粒溶于丙酮与N，N-二甲基甲酰胺中，通过转速为400r/min机械球磨30h得到混合溶液，然后将上述混合溶液缓慢浇注到聚四氟乙烯模具中，再进行辊压厚度为60μm，放入温度为80℃的真空干燥箱静置24h以去除上述有机溶剂，得到复合固态电解质膜。
本实施例对所述复合固态电解质进行物理及电化学测试，与未处理的相比具有相对较低阻抗和极化，以及较长的循环寿命。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何背离本发明的精神实质与原理下做的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种等离子体改性钠超离子导体型固态电解质的方法，其特征在于，具体包括以下步骤：
    等离子体改性处理：对钠超离子导体型固态电解质颗粒进行等离子体改性处理，得到活化钠超离子导体型固态电解质颗粒。
    复合固态电解质的制备：按照预订的比例称取聚合物与所述活化钠超离子导体型固态电解质颗粒，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于有机溶剂中得到混合溶液，然后将所述混合溶液浇注到预设模具中，再进行干燥以去除所述有机溶剂并成形为复合固态电解质膜，从所述预设模具中取出所述复合固态电解质膜并进行辊压，得到辊压处理后的复合固态电解质膜。
  2. 根据权利要求1所述的方法，其特征在于：对所述钠超离子导体型固态电解质颗粒进行等离子体改性处理的步骤中，所述等离子体改性处理采用预设等离子体气氛、预设气体流速、预设电压、预设电流及第一预设时间，所述预设等离子体气氛为氮气、氧气、氩气、氮氧混合气、氮氩混合气、空气中的一种或几种，所述预设等离子体气氛的压强为大气压，所述预设电压为施加在所述钠超离子导体型固态电解质颗粒的电压且电压范围为10V～150V，所述预设电流为施加在所述钠超离子导体型固态电解质颗粒的电流且电流范围为0.2A～2A，所述第一预设时间为1min～60min。
  3. 根据权利要求1所述的方法，其特征在于：预设比例为所述聚合物与所述活化钠超离子导体型固态电解质颗粒质量比例，所述质量比例的范围为10wt.％～80wt.％。
  4. 根据权利要求1所述的方法，其特征在于：所述聚合物种类包括聚氧化乙烯、聚偏氟乙烯、、聚偏二氟乙烯-co-六氟丙烯、聚乙二醇中的至少一种。
  5. 根据权利要求1所述的方法，其特征在于：所述有机溶剂包括丙酮、N，N-二甲基甲酰胺、乙腈、N-甲基吡咯烷酮中的一种或两种。
  6. 根据权利要求1所述的方法，其特征在于：所述将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于所述有机溶剂得到混合溶液的步骤中，将所述聚合物与所述活化钠超离子导体型固态电解质颗粒溶于所述有机溶剂并进行机械球磨得到所述混合溶液。
  7. 根据权利要求6所述的方法，其特征在于：所述机械球磨在预定机械球磨转速下进行，所述预定机械球磨转速范围为150r/min～400r/min；所述 机械球磨的时间为第二预设时间，所述第二预设时间的范围为5h～48h。
  8. 根据权利要求1所述的方法，其特征在于：所述将所述混合溶液浇注到预设模具中，再进行干燥以去除所述有机溶剂并成形为复合固态电解质膜的步骤包括：将所述混合溶液浇注到所述预设模具中，并放入真空干燥箱，然后将所述真空干燥箱中的温度调节至预设温度并保持第三预设时间从而得到所述复合固态电解质膜；所述第三预设时间的范围为15h～48h；所述预设温度的范围为40℃～100℃。
  9. 根据权利要求1所述的方法，其特征在于：所述辊压处理后的复合固态电解质膜的厚度为30μm～100μm。
  10. 一种等离子体改性钠超离子导体型固态电解质的方法，其包括如下步骤:
    对钠超离子导体型固态电解质颗粒进行等离子体活化处理，得到活化钠超离子导体型固态电解质颗粒；
    利用所述活化钠超离子导体型固态电解质颗粒获取复合固态电解质膜，所述复合固态电解质膜的厚度为30μm～100μm。
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