CN114188601A - Preparation method and application of solid electrolyte - Google Patents
Preparation method and application of solid electrolyte Download PDFInfo
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- CN114188601A CN114188601A CN202111507790.9A CN202111507790A CN114188601A CN 114188601 A CN114188601 A CN 114188601A CN 202111507790 A CN202111507790 A CN 202111507790A CN 114188601 A CN114188601 A CN 114188601A
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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
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention relates to the technical field of solid electrolytes, in particular to a preparation method and application of a solid electrolyte. The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps: firstly mixing sodium-containing salt, phosphorus-containing salt, zirconium oxide and silicon oxide, and calcining to obtain a silicon-zirconium-sodium phosphate precursor; and secondly, mixing the silicon zirconium sodium phosphate precursor, the binder and sodium metasilicate, and then sequentially performing tabletting and liquid phase sintering to obtain the solid electrolyte. The solid electrolyte prepared by the preparation method has a wider electrochemical window.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a preparation method and application of a solid electrolyte.
Background
Lithium ion batteries have rapidly developed over the past decade. However, the price increase hinders further applications of lithium ion batteries, and it is imperative to find cheaper batteries to replace lithium ion batteries. Sodium ion batteries are considered to be the best energy storage device to replace lithium ion batteries due to their abundant sodium resources and low cost. Unlike organic liquid electrolytes, which are easily leaked, flammable, and ineffective in suppressing dendrites, solid sodium electrolytes are widely used in sodium metal batteries to improve safety.
Many types of solid sodium electrolytes, such as beta-alumina type, sulfide type and sodium super-ionic conductor type, have been studied so far. The practical application of the beta-alumina type is limited by the extremely high sintering temperature (1200-1500 ℃) of the beta-alumina type and the instability of sulfides in air. However, sodium super-ionic conductor type solid electrolytes such as sodium silico-zirconium phosphate can be an attractive material due to their relatively low sintering temperature, stability in air, good ionic conductivity and low thermal expansion.
The conventional preparation method for preparing the sodium super-ionic conductor type solid electrolyte generally adopts a solid-phase sintering method, and although the obtained sodium super-ionic conductor type solid electrolyte has better ionic conductivity, the electrochemical window is narrower.
Disclosure of Invention
The invention aims to provide a preparation method and application of a solid electrolyte, and the solid electrolyte prepared by the preparation method has a wider electrochemical window.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a solid electrolytic cell, which comprises the following steps:
firstly mixing sodium-containing salt, phosphorus-containing salt, zirconium oxide and silicon oxide, and calcining to obtain a silicon-zirconium-sodium phosphate precursor;
and secondly, mixing the silicon zirconium sodium phosphate precursor, the binder and sodium metasilicate, and then sequentially performing tabletting and liquid phase sintering to obtain the solid electrolyte.
Preferably, the molar ratio of sodium in the sodium-containing salt, zirconium in the zirconium oxide, silicon in the silicon oxide and phosphorus in the phosphorus-containing salt is 3:2:2: 1.05.
Preferably, the first mixing mode is ball milling;
the ball-material ratio of the ball mill is (4-6): 1, the rotation speed is 300-500 rpm, and the time is 5-12 h.
Preferably, the calcining temperature is 900-1100 ℃, the heat preservation time is 12-24 h, and the heating rate of heating to the calcining temperature is 5-10 ℃/min.
Preferably, the mass ratio of the silicon zirconium sodium phosphate precursor to the sodium metasilicate is 100: (1-10).
Preferably, the binder is a polyvinyl alcohol aqueous solution with the mass concentration of 3-5%;
the volume ratio of the total mass of the silicon zirconium sodium phosphate precursor to the sodium metasilicate to the polyvinyl alcohol aqueous solution is (500-600) mg: (50-100) mu L.
Preferably, the second mixing comprises mixing and ball-milling the zirconium sodium silicophosphate precursor and sodium metasilicate, and then mixing with a binder;
the mixing ball milling mode is wet ball milling;
the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, the rotation speed is 300-500 rpm, and the time is 5-12 h.
Preferably, the pressure of the tabletting is 150-250 MPa, and the pressure maintaining time is 3-5 min.
Preferably, the liquid phase sintering comprises a first sintering and a second sintering which are sequentially carried out;
the temperature of the first sintering is 600-800 ℃, and the time is 2-4 h;
the temperature of the second sintering is 1000-1200 ℃, and the time is 12-24 h.
The invention also provides application of the solid electrolyte prepared by the preparation method in the technical scheme in a sodium ion battery, wherein the solid electrolyte comprises Na3Zr2Si2PO12。
The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps: firstly mixing sodium-containing salt, phosphorus-containing salt, zirconium oxide and silicon oxide, and calcining to obtain a silicon-zirconium-sodium phosphate precursor; and secondly, mixing the silicon zirconium sodium phosphate precursor, the binder and sodium metasilicate, and then sequentially performing tabletting and liquid phase sintering to obtain the solid electrolyte. According to the invention, a plurality of small holes are reserved after sintering of the electrolyte obtained by using the binder tablet, and the holes are filled with liquid-phase sodium metasilicate, so that the surface of the zirconium sodium silicophosphate electrolyte has excellent anode stability, and a wider electrochemical window is obtained; meanwhile, when the prepared solid electrolyte is used as the electrolyte of the sodium ion battery, the liquid phase sintering is adopted, so that the transmission of sodium ions can be faster, the sodium deposited on an interface is reduced, the embedding and the de-embedding of the sodium are more uniform, and the possibility of generating sodium dendrite is reduced. Micro short circuit is less likely to occur in the electrolyte, and the cycle performance can be effectively improved.
Drawings
FIG. 1 is an SEM photograph of a solid electrolyte as described in example 1;
FIG. 2 is an XRD pattern of the solid state electrolyte described in example 1;
FIG. 3 is a graph of the AC impedance of the solid electrolyte of example 1;
FIG. 4 is a diagram of the electrochemical window of the solid electrolyte of example 1;
FIG. 5 is a polarization plot of the solid electrolyte described in example 1;
FIG. 6 is an SEM photograph of the solid electrolyte described in comparative example 1;
fig. 7 is an XRD pattern of the solid electrolyte described in comparative example 1;
FIG. 8 is a graph showing the AC impedance of the solid electrolyte of comparative example 1;
FIG. 9 is a diagram of an electrochemical window of the solid electrolyte described in comparative example 1;
FIG. 10 is a polarization diagram of the solid electrolyte described in comparative example 1;
FIG. 11 is a graph showing the cycling performance of a symmetrical cell prepared with the solid electrolyte described in example 1;
FIG. 12 is a graph showing the cycle performance of a half cell prepared from the solid electrolyte described in example 1;
FIG. 13 is a graph showing the cycling performance of a symmetrical cell prepared from the solid electrolyte described in comparative example 1;
fig. 14 shows the cycle performance of the half cell prepared from the solid electrolyte described in comparative example 1.
Detailed Description
The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps:
firstly mixing sodium-containing salt, phosphorus-containing salt, zirconium oxide and silicon oxide, and calcining to obtain a silicon-zirconium-sodium phosphate precursor;
and secondly, mixing the silicon zirconium sodium phosphate precursor, the binder and sodium metasilicate, and then sequentially performing tabletting and liquid phase sintering to obtain the solid electrolyte.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
According to the invention, after sodium salt, phosphorus salt, zirconium oxide and silicon oxide are firstly mixed, calcination is carried out, and the precursor of silicon zirconium sodium phosphate is obtained.
In the present invention, the sodium-containing salt is preferably sodium carbonate. The phosphorus-containing salt is preferably ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; when the phosphorus-containing salt is more than two of the specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. The zirconium oxide is preferably zirconium dioxide. The silicon oxide is preferably silicon dioxide.
In the present invention, the molar ratio of sodium in the sodium-containing salt, zirconium in the zirconium oxide, silicon in the silicon oxide, and phosphorus in the phosphorus-containing salt is preferably 3:2:2: 1.05.
In the present invention, the first mixing method is preferably ball milling; the ball-material ratio of the ball milling is preferably (4-6): 1, more preferably (4.5 to 5.5): 1, most preferably (4.8-5.2): 1; the rotation speed is preferably 300-500 rpm, more preferably 350-450 rpm, and most preferably 380-420 rpm; the time is preferably 5 to 12 hours, more preferably 6 to 10 hours, and most preferably 7 to 9 hours. In the invention, the ball milling is preferably wet ball milling, and the ball milling medium of the wet ball milling is preferably ethanol; the amount of ethanol used in the present invention is not particularly limited, and may be any amount known to those skilled in the art by wet ball milling.
In the present invention, the ball milling is preferably carried out in a planetary ball mill.
In the invention, the ball milling conditions can ensure that the mixed material obtained after mixing has finer particle size and more uniform mixing, thereby being beneficial to more thorough reaction of the powder obtained by subsequent sintering.
After the first mixing is completed, the present invention also preferably includes drying, preferably vacuum drying; the temperature of the vacuum drying is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 12 to 24 hours, more preferably 15 to 20 hours, and most preferably 16 to 18 hours.
In the invention, the calcination temperature is preferably 900-1100 ℃, more preferably 950-1050 ℃, and most preferably 980-1020 ℃; the heat preservation time is preferably 12-24 h, more preferably 15-20 h, and most preferably 16-18 h; the heating rate for heating to the calcination temperature is preferably 5-10 ℃/min, and more preferably 6-8 ℃/min.
After the calcination is completed, the present invention preferably further comprises cooling, and the cooling process is not limited in any way, and the cooling process known to those skilled in the art can be used to cool the catalyst to room temperature. In a particular embodiment of the invention, the cooling is preferably furnace cooling.
After said cooling is complete, the present invention also preferably includes grinding; the rotation speed of the grinding is not limited in any way in the present invention, and the grinding is performed by a process well known to those skilled in the art, and the grinding time is preferably 15 min.
In the present invention, the sodium silicozirconium phosphate precursor includes sodium silicozirconium phosphate and unreacted zirconium dioxide.
After obtaining the silicon zirconium sodium phosphate precursor, the invention mixes the silicon zirconium sodium phosphate precursor, the binder and the sodium metasilicate for the second time, and then carries out tabletting and liquid phase sintering in sequence to obtain the solid electrolyte.
In the invention, the binder is preferably a polyvinyl alcohol aqueous solution with the mass concentration of 3-5%, and the mass concentration of the polyvinyl alcohol aqueous solution is more preferably 5%; the polyvinyl alcohol aqueous solution is preferably prepared by mixing polyvinyl alcohol and water to obtain the polyvinyl alcohol aqueous solution. In the present invention, the mixing is preferably performed under the conditions of oil bath and stirring; the temperature of the oil bath is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 0.5 to 1.5 hours, and more preferably 0.8 to 1.2 hours. The stirring rate is not particularly limited in the present invention, and may be carried out at a rate known to those skilled in the art.
In the invention, the addition of the binder can make the electrolyte sheet become more compact under the same pressure, thereby reducing the sintering temperature; the addition of the binder can enable the surface of the electrolyte to have excellent positive stability, thereby obtaining a wider electrochemical window; meanwhile, the use of the binder can also effectively improve the strength of the unsintered electrolyte sheet, so that the electrolyte sheet can be formed into a compact electrolyte sheet only by low pressure, and the industrial production is facilitated.
In the invention, the volume ratio of the total mass of the silicon zirconium sodium phosphate precursor and the sodium metasilicate to the polyvinyl alcohol aqueous solution is preferably (500-600) mg: (50-100) μ L, more preferably (510-560) mg: (60-90) μ L, most preferably (520-540) mg: (70-80) mu L.
In the present invention, the mass ratio of the zirconium sodium silicophosphate precursor to sodium metasilicate is preferably 100: (1-10), more preferably 100: (2-8), most preferably 100: (5).
In the invention, in the sintering process, besides the sodium metasilicate is melted into a liquid phase at high temperature, the crystal grains of the silicon zirconium sodium phosphate can be more compact, and the density of the electrolyte is improved; simultaneously, the sodium metasilicate is added, so that the sodium metasilicate can be melted at the crystal boundary of the silicon zirconium sodium phosphate in the subsequent sintering process, and sodium and silicon elements are diffused to crystal grains of the silicon zirconium sodium phosphate; meanwhile, by further adjusting the proportion of the silicon zirconium sodium phosphate element, a sodium ion transmission channel is adjusted, the activation energy is reduced, and the ionic conductivity of the electrolyte is greatly improved.
In the present invention, the second mixing preferably includes mixing and ball-milling the zirconium sodium silicophosphate precursor and sodium metasilicate, and then mixing with a binder.
Before the mixing and ball milling, the method also preferably comprises grinding, wherein the grinding time is preferably 5-15 min, and more preferably 8-12 min; the rotation speed of the grinding is not particularly limited in the present invention, and may be a rotation speed known to those skilled in the art.
In the invention, the mixing ball milling mode is wet ball milling; the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, more preferably (4.5 to 5.5): 1, most preferably (4.8-5.2): 1; the rotation speed is preferably 300-500 rpm, more preferably 350-450 rpm, and most preferably 380-420 rpm; the time is preferably 5 to 12 hours, more preferably 6 to 10 hours, and most preferably 7 to 9 hours. The amount of ethanol used in the present invention is not particularly limited, and may be any amount known to those skilled in the art by wet ball milling.
After the mixing and ball milling is completed, the present invention also preferably includes drying. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 12 to 24 hours, and more preferably 15 to 20 hours.
In the present invention, the mixing with the binder is preferably performed by grinding; the grinding process is not limited in any way, and the grinding process is carried out by adopting a process well known to those skilled in the art, and the binder is completely coated on the surface of the particles (the mixed material of the silicon zirconium sodium phosphate precursor and the sodium metasilicate).
In the invention, the pressure of the tabletting is preferably 150-250 MPa, more preferably 180-220 MPa, and most preferably 200 MPa; the dwell time is preferably 3 to 5min, more preferably 3.5 to 4.5min, and most preferably 4 min.
In the present invention, the liquid phase sintering is preferably performed in an air atmosphere or an oxygen atmosphere; the liquid phase sintering preferably includes a first sintering and a second sintering which are performed in this order; the first sintering temperature is preferably 600-800 ℃, more preferably 650-750 ℃, and most preferably 680-720 ℃; the time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 3 hours; the temperature of the second sintering is preferably 1000-1200 ℃, and more preferably 1050-1150 ℃; the time is preferably 12 to 24 hours, and more preferably 15 to 18 hours.
After the liquid phase sintering is complete, the present invention also preferably includes cooling. The cooling method of the present invention is not particularly limited, and may be performed in a manner known to those skilled in the art. In a particular embodiment of the invention, the cooling is in particular furnace cooling.
The invention also provides application of the solid electrolyte prepared by the preparation method in the technical scheme in a sodium ion battery, wherein the solid electrolyte comprises Na3Zr2Si2PO12. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following examples are provided to illustrate the preparation and application of the solid electrolyte of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Placing 0.9937g of sodium carbonate, 1.5403g of zirconium dioxide, 0.7511g of silicon dioxide and 0.7548g of ammonium dihydrogen phosphate into a planetary ball mill, adding 24g of zirconium oxide balls and 4mL of ethanol, and carrying out mixed ball milling at the rotation speed of 400rpm for 12 hours; vacuum drying at 80 ℃ for 12h, calcining at 1000 ℃ for 12h in air atmosphere, cooling to room temperature, and grinding for 15min to obtain a silicon-zirconium-sodium phosphate precursor;
mixing 1.025g of polyvinyl alcohol and 23.75g of deionized water, and carrying out oil bath at 80 ℃ for 1h under the condition of stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
putting 3.2g of the zirconium silicophosphate sodium precursor and 0.16g of sodium metasilicate (5 percent of the zirconium silicophosphate precursor) into a planetary ball mill, adding 24g of zirconia and 4mL of ethanol, and carrying out ball milling, wherein the rotating speed of the ball milling is 400rpm, and the time is 12 hours; vacuum drying at 80 deg.C for 12 hr to obtain mixed material;
grinding 530mg of the mixed material and 50 mu L of polyvinyl alcohol aqueous solution until the polyvinyl alcohol aqueous solution is completely coated on the surface of the particles, pouring the particles into a mould with the diameter of 16mm, and pressing the particles for 4min under 150MPa to obtain an electrolyte sheet with the thickness of 1.2 mm;
sequentially carrying out first sintering and second sintering on the electrolyte sheet; the temperature of the first sintering is 800 ℃, and the time is 4 hours; the temperature of the second sintering is 1100 ℃, the time is 12 hours, and the solid electrolyte (the ionic conductivity is 1.80 multiplied by 10) is obtained after cooling-4S·cm-1Electrochemical window of 4.83V, electronic conductivity of 6.24X 10–7S·cm–1The transference number of sodium ions is 0.9965);
performing SEM test and XRD test on the solid electrolyte, wherein the test results are shown in figures 1-2, wherein figure 1 is an SEM image of the solid electrolyte, and figure 2 is an XRD image of the solid electrolyte; as can be seen from FIGS. 1-2, the solid electrolyte sheet has a compact structure and no impurity phase is generated;
FIG. 3 is a diagram of the AC impedance of the solid electrolyte, and it can be seen from FIG. 3 that the semicircular part is the high frequency region, and the diagonal part is the low frequency region, where the impedance of the electrolyte can be obtained from the boundary between the high frequency and the low frequency in the diagram to be 331 Ω;
FIG. 4 is a diagram showing an electrochemical stability window of the solid electrolyte, and it can be seen from FIG. 4 that the electrochemical stability window is 4.83V as seen from the abscissa of the intersection of the horizontal line and the oblique line;
fig. 5 is a polarization curve of the solid electrolyte, and it can be seen from fig. 5 that the current when reaching the steady state is 0.104 μ a.
Comparative example 1
Placing 0.9937g of sodium carbonate, 1.5403g of zirconium dioxide, 0.7511g of silicon dioxide and 0.7548g of ammonium dihydrogen phosphate into a planetary ball mill, adding 24g of zirconium oxide balls and 4mL of ethanol, and carrying out mixed ball milling at the rotation speed of 400rpm for 12 hours; vacuum drying at 80 ℃ for 12h, calcining at 1000 ℃ for 12h in air atmosphere, cooling to room temperature, and grinding for 15min to obtain a silicon-zirconium-sodium phosphate precursor;
mixing 1.25g of polyvinyl alcohol and 23.75g of deionized water, and carrying out oil bath at 80 ℃ for 1h under the condition of stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
putting 3.2g of the sodium silicozirconium phosphate precursor into a planetary ball mill, adding 24g of zirconium oxide and 4mL of ethanol, and carrying out ball milling, wherein the rotating speed of the ball mill is 400rpm, and the time is 12 hours; vacuum drying at 80 ℃ for 12h to obtain the ball grinding material;
grinding 530mg of the ball grinding material and 50 mu L of polyvinyl alcohol aqueous solution until the polyvinyl alcohol aqueous solution is completely coated on the surface of the particles, pouring the particles into a mould with the diameter of 16mm, and pressing the particles for 4min under 150MPa to obtain an electrolyte sheet with the thickness of 1.2 mm;
sequentially carrying out first sintering and second sintering on the electrolyte sheet; the temperature of the first sintering is 800 ℃, and the time is 4 hours; the temperature of the second sintering is 1100 ℃, the time is 12 hours, and the solid electrolyte (the ionic conductivity is 5.12 multiplied by 10) is obtained after cooling-5S·cm-1Electrochemical window of 4.50V and electronic conductivity of 7.41X 10-7S·cm–1The transference number of sodium ions is 0.9855);
performing SEM test and XRD test on the solid electrolyte, wherein the test results are shown in figures 6-7, wherein figure 6 is an SEM image of the solid electrolyte, and figure 7 is an XRD image of the solid electrolyte; as can be seen from fig. 6 to 7, the crystal grains in the solid electrolyte sheet are small and there is impurity phase zirconium dioxide;
fig. 8 is an ac impedance diagram of the solid electrolyte, and as can be seen from fig. 3, the semicircular part is a high frequency region, and the diagonal part is a low frequency region, where the impedance of the electrolyte can be obtained from the boundary between the high frequency and the low frequency in the diagram, which is 1166 Ω;
FIG. 9 is a diagram showing an electrochemical stability window of the solid electrolyte, and as can be seen from FIG. 4, the horizontal line and the oblique line are respectively tangent, and an electrochemical stability window of 4.50V can be obtained from the abscissa of the intersection point;
fig. 10 is a polarization curve of the solid electrolyte, and it can be seen from fig. 5 that the current when reaching the steady state is 0.124 μ a.
In conclusion, the preparation method provided by the invention can obviously improve the ionic conductivity, the electrochemical window and the sodium ion migration number of the solid electrolyte.
Test example 1
The solid electrolyte described in example 1 was placed in two sodium tablets 14mm in diameter and 0.7mm in thicknessIn the CR2032 battery case, the order is sodium sheet-electrolyte-sodium sheet. The cell was pressed into a symmetrical cell under a pressure of 12.5MPa, and then the cell was tested at 0.1 mA-cm-2And 0.1mAh · cm-2The cycle performance of (c). The test results are shown in fig. 11. The symmetric cell remained stable after 400h cycling, showing stable intercalation and deintercalation of sodium.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, adding 980mg of N-methyl pyrrolidone, stirring for 5 hours, and pouring the slurry onto an aluminum foil. After drying, the obtained product was cut into 14mm round positive plates, and the loading of active material in each positive plate was 1.84 mg. The positive plate, the liquid phase sintered electrolyte and a sodium plate with the diameter of 14mm and the thickness of 0.7mm are placed in a CR2025 battery shell, and the positive plate-electrolyte-sodium plate is arranged in sequence. Applying pressure of 12.5MPa to press the battery into a half battery, and then testing the cycle performance of the battery under the current density of 0.1C and the voltage range of 2.0-4.0V. The test results are shown in fig. 12: the capacity of the half cell after 100 cycles at 0.1C was 92.4mAh g-1The capacity retention rate is as high as 96.6%.
Test example 2
The electrolyte obtained by solid phase sintering and two sodium sheets with the diameter of 14mm and the thickness of 0.7mm are placed in a CR2032 battery case, and the two sheets are sequentially sodium sheet-electrolyte-sodium sheet. The cell was pressed into a symmetrical cell under a pressure of 12.5MPa, and then the cell was tested at 0.1 mA-cm-2And 0.1mAh · cm-2The cycle performance of (c). The test results are shown in fig. 13. The symmetric cell shows unstable polarization only in 35h, and the polarization voltage is as high as 0.735V, which indicates that the insertion and extraction of sodium in the symmetric cell are unstable.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, adding 980mg of N-methyl pyrrolidone, stirring for 5 hours, and pouring the slurry onto an aluminum foil. After drying, the obtained product was cut into 14mm round positive plates, and the loading of active material in each positive plate was 1.84 mg. The positive plate, the solid-phase sintered electrolyte and a sodium plate with the diameter of 14mm and the thickness of 0.7mm are placed in a CR2025 battery case, and the positive plate-electrolyte-sodium plate is arranged in sequence. Applying a pressure of 12.5MPa to press the semi-cell, and then testing the cell at a current density of 0.1C and a voltage range of 2.0-4.0VCycle performance under the enclosure. The test results are shown in fig. 12: the capacity of the half cell after 100 times of circulation at 0.1 ℃ is 86.9mAh g-1The capacity retention rate is 95.9%, which is lower than that of a half cell assembled by liquid phase sintering electrolyte.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method of making a solid state electrolytic cell, comprising the steps of:
firstly mixing sodium-containing salt, phosphorus-containing salt, zirconium oxide and silicon oxide, and calcining to obtain a silicon-zirconium-sodium phosphate precursor;
and secondly, mixing the silicon zirconium sodium phosphate precursor, the binder and sodium metasilicate, and then sequentially performing tabletting and liquid phase sintering to obtain the solid electrolyte.
2. The method of claim 1, wherein the molar ratio of sodium in the sodium-containing salt, zirconium in the zirconium oxide, silicon in the silicon oxide, and phosphorus in the phosphorus-containing salt is 3:2:2: 1.05.
3. The method of claim 1, wherein the first mixing is by ball milling;
the ball-material ratio of the ball mill is (4-6): 1, the rotation speed is 300-500 rpm, and the time is 5-12 h.
4. The preparation method according to claim 1, wherein the calcination temperature is 900 to 1100 ℃, the holding time is 12 to 24 hours, and the temperature rise rate for raising the temperature to the calcination temperature is 5 to 10 ℃/min.
5. The method according to claim 1, wherein the mass ratio of the sodium zirconium silicophosphate precursor to the sodium metasilicate is 100: (1-10).
6. The preparation method according to claim 1, wherein the binder is a polyvinyl alcohol aqueous solution with a mass concentration of 3-5%;
the volume ratio of the total mass of the silicon zirconium sodium phosphate precursor to the sodium metasilicate to the polyvinyl alcohol aqueous solution is (500-600) mg: (50-100) mu L.
7. The method of claim 1, 5 or 6, wherein the second mixing comprises mixing and ball milling the zirconium sodium silicophosphate precursor and sodium metasilicate, and mixing with a binder;
the mixing ball milling mode is wet ball milling;
the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, the rotation speed is 300-500 rpm, and the time is 5-12 h.
8. The method according to claim 1, wherein the pressure of the compressed tablet is 150 to 250MPa, and the dwell time is 3 to 5 min.
9. The production method according to claim 1, wherein the liquid phase sintering includes a first sintering and a second sintering which are performed in this order;
the temperature of the first sintering is 600-800 ℃, and the time is 2-4 h;
the temperature of the second sintering is 1000-1200 ℃, and the time is 12-24 h.
10. Use of the solid electrolyte prepared by the preparation method of any one of claims 1 to 9 in a sodium ion battery, wherein the solid electrolyte comprises Na3Zr2Si2PO12。
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