CN107565157B - Microporous nanocrystalline sodium ion solid electrolyte and preparation method thereof - Google Patents
Microporous nanocrystalline sodium ion solid electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion battery electrolytes,relates to a microporous nanocrystalline sodium ion solid electrolyte and a preparation method thereof, wherein the microporous nanocrystalline sodium ion solid electrolyte comprises the following raw materials in percentage by mole: 20-60% of phosphoric acid, 10-30% of titanate and 20-40% of sodium salt, wherein the sum of the mole percentages is 100%; wherein phosphoric acid is H3PO4(85 wt%); the titanium compound is tetrabutyl titanate, titanium tetrachloride and barium titanate; the sodium salts include: sodium acetate, sodium phosphate, disodium hydrogen phosphate, sodium acetate and sodium carbonate. The preparation method comprises the following steps: 1) preparing a microporous nanocrystalline miscible substance; 2) carrying out crystallization treatment on the microporous nanocrystalline sodium ion electrolyte; 3) and (3) hot-press molding of the microporous nanocrystalline. The microporous nanocrystalline solid electrolyte NaTi prepared by the method2(PO4)3Has a temperature of up to 1.071 × 10‑3S·cm‑1High ionic conductivity and high stability. Compared with the reported method, the preparation process of the invention is very simple, the reaction temperature is lower, the reaction time is short, and the invention is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of sodium ion battery electrolytes, in particular to a microporous nanocrystalline sodium ion solid electrolyte and a preparation method thereof, and mainly provides a new material for the energy field of electric automobiles and the like.
Background
At present, wind power, hydropower, nuclear energy and the like are paid more and more attention, and the progress of the power generation technology leads to the continuous glide of power storage in a busy season, thereby promoting the vigorous development of energy storage materials. Among them, the shortage of lithium resources and the potential risk factors have forced researchers to develop high-safety, low-cost, high-specific-energy batteries. Therefore, in recent years, all-solid-state sodium ion batteries have been proposed. Compared with other energy storage technologies, the all-solid-state sodium ion battery has the advantages of rich resources, low cost, high half-cell potential, stable electrochemical performance and the like. At present, sodium-sulfur batteries are representative of successful applications of sodium-ion batteries; however, higher operating temperatures can lead to high operating costs and potential safety issues. Therefore, the development of room-temperature all-solid-state sodium ion batteries for large-scale application has very important strategic significance. The all-solid sodium ion electrolyte is an important component of the all-solid battery, and determines the safety, electrochemical performance, cycle life and energy density of the all-solid battery. Therefore, the sodium ion electrolyte, which is an essential component of the all-solid-state sodium ion battery, needs to satisfy the following requirements: high ionic conductivity at high ambient temperature, wide electrochemical window, high electrochemical stability, high thermal stability and mechanical strength, etc.
Main set of research in the past decadeSolid Polymer Electrolytes (SPE), inorganic solid composite electrolytes with NASICON structured glass ceramic electrolytes and amorphous solid electrolytes. In 2013, V.B.Nalbandyman synthesizes a novel Na through solid-phase reaction at 700 DEG C2LiFeTeO6Materials exhibiting a high 4X 10 at 300 deg.C-2S·m-1The ionic conductivity of (a). In 2015, Jae Chul Kim prepared cube Na using cold pressing technique3PSe4The ionic conductivity of the material reaches 1.1 x 10 at room temperature-4S·cm-1This is due to the weakening of some of the interfacial reactions caused by high temperature sintering by cold pressing. In 2017, Jianan Luo proposed a NASICON material, Na3+2xZr2xMxSi2PO12(M＝Mg2+，Ni2+) Total ionic conductivity of 2.7X 10 at room temperature-3S·cm-1. However, the temperature of the preparation process is 1150-1300 ℃, the whole preparation process needs more than 100 hours, and the synthesis method is complex. NASICON type NaTi2(PO4)3(NTP) theoretical capacity up to 133mAh g-1And the sodium ion has high conductivity and better thermal stability, and is often used as an SIB electrode. However, NTP has been rarely reported as an electrolyte. Therefore, the invention provides a novel microporous nanocrystalline sodium ion solid electrolyte and a preparation method thereof, and the prepared microporous nanocrystalline solid electrolyte NaTi2(PO4)3Has high room temperature ionic conductivity and stability, and the ionic conductivity at room temperature can reach up to 1.071 multiplied by 10-3S·cm-1. Compared with the reported method, the preparation process of the invention is very simple, the reaction temperature is lower, the reaction time is short, and the method is suitable for large-scale production. All these indicate that microporous NTP will have potential applications in solid electrolytes.
Disclosure of Invention
The technical problem is as follows: the invention provides a microporous nanocrystalline solid electrolyte with high conductivity and high stability and a preparation method thereof. The microporous nanocrystalline solid electrolyte disclosed by the invention utilizes the advantages of abundant and easily available sodium ions, low cost and the like to furthest relieve the problem of shortage of lithium ore resources, achieves the purpose of use at room temperature, and can be produced in batches. The specific technical scheme of the invention is as follows:
the technical scheme is as follows: the invention provides a microporous nanocrystalline sodium ion solid electrolyte, which comprises the following raw materials in percentage by mole: 20-60% of phosphoric acid, 10-30% of titanium compound and 20-40% of sodium salt, and the sum of the mole percentages is 100%.
Wherein the phosphoric acid is 85 wt% of H3PO4(ii) a The titanium compound is selected from one or a mixture of tetrabutyl titanate, titanium tetrachloride and barium titanate; the sodium salt is selected from one or more of sodium acetate, sodium phosphate, disodium hydrogen phosphate, sodium acetate, and sodium carbonate.
The invention also provides a preparation method of the fear-only nanocrystalline sodium ion solid electrolyte, which comprises the following steps: 1) preparing a microporous nanocrystalline miscible substance: 2) crystallization treatment of microporous nanocrystalline sodium ion electrolyte: 3) and (3) hot-press molding of the microporous nanocrystalline. The method comprises the following specific steps:
1) preparing a microporous nanocrystalline miscible substance: dissolving sodium salt and concentrated phosphoric acid in an organic solvent to obtain a mixed solution A; dissolving a titanium compound in an organic solvent to obtain a titanium compound organic solution, dropwise adding the mixed solution A into the titanium compound organic solution, and stirring for 5-8min after dropwise adding to obtain a microporous nanocrystal miscible substance preparation solution;
and (2) continuously increasing the stirring speed in the dripping process according to the change of the solution color from clear to opaque, and properly reducing the stirring speed to continue stirring after the color is lightened.
In the step (1), the organic solvent is absolute ethyl alcohol.
2) Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: sealing the mixed solution in a reaction kettle, reacting the reaction kettle at the temperature of 120-200 ℃ for 2-8h to ensure that crystals grow uniformly, controlling the size of crystal grains to be 50-300nm, washing and drying to obtain the titanium sodium phosphate microporous nanocrystalline;
in the step 2), the prepared titanium sodium phosphate microporous nanocrystalline needs to be ground for 30min to obtain titanium phosphate microporous nanocrystalline powder.
The reaction temperature in the step 2) is 120-200 ℃, preferably 135-140 ℃, and the reaction time is 2-8h, preferably 2-4 h.
3) Hot-press molding of the microporous nanocrystalline: adding the sodium titanium phosphate microporous nanocrystalline powder into a designed mold, molding by using a vacuum hot-pressing technology, and controlling the hot-pressing temperature within the range of 100-600 ℃, the pressure within the range of 20-70MPa and the time within 0.5-3 h.
In order to obtain higher conductivity, the invention adopts the reaction condition of 135-140 ℃ for reaction for 2-4h, so that the micropore nano crystal sodium ion electrolyte is more uniformly crystallized, the crystal growth is more controllable, the crystal boundary resistance is reduced, and the sodium ion mobility is improved.
In the crystallization process of step 2), the reaction temperature and the reaction time need to be accurately controlled, so as to realize the controllable growth of the microporous nanocrystals. Research shows that the grain size has direct relation with the conductivity, the conductivity can reach 2.467 × 10 within the range of 160-200nm-4S·cm-1(ii) a When the grain size is 100-140nm, the conductivity can reach 2.594 multiplied by 10-4S·cm-1The conductivity has no obvious change; when the grain size is 60-120nm, the conductivity can reach 1.061 multiplied by 10-3S·cm-1The conductivity is obviously improved by one order of magnitude; however, as the grain size continues to decrease, at 60-100nm, the conductivity is 5.093X 10-4S·cm-1(ii) a The conductivity will decrease again, so accurate control of the reaction temperature and reaction time is of great significance in controlling the size and conductivity of the microporous nanocrystal.
The purpose of hot-press molding is as follows: the first is to exhaust air and water vapor in the electrolyte when assembling the battery; secondly, manufacturing the required shape and size according to the requirement; thirdly, the electrolyte material is more compact and dense to the maximum extent, the resistance among particles is reduced, and the lattice structure after hot press molding at a high temperature state is more stable.
Through testing, the crystal in the microporous nanocrystalline sodium ion solid electrolyte is determined to be an orthorhombic NaTi2(PO4)3By applying electricity theretoSimulation analysis of charge density distribution shows that: in the unit cell, the central sodium ion (O) is bound by two TiO8Octahedral enclosure, six POs4A tetrahedron. In the perspective view of FIG. 3, sodium ions (O) are located in the region formed by TiO8Octahedron and six POs4In the middle of the irregular hexagon composed of tetrahedral oxygen, each sodium ion has three-directional migration channels, and the sodium ions pass through the channels and move in a migration mode.
In the experimental operation, the steps of preparing the microporous nanocrystalline sodium ion solid electrolyte can be specifically as follows:
1) preparing a microporous nanocrystalline miscible substance: the first step is as follows: weighing sodium salt, putting into a small beaker, adding concentrated phosphoric acid and some absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium salt is completely dissolved. The second step is that: firstly, adding some absolute ethyl alcohol into a large beaker, then dropwise adding the weighed titanium compound, uniformly stirring by using a magnetic stirrer, and continuously adding the absolute ethyl alcohol to a constant volume. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the color of the mixed solution from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 5-8min after the dripping is finished; and obtaining the microporous nanocrystalline miscible liquid preparation.
2) Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: the uniformly mixed miscible liquid is divided into two parts and put into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, the cover is screwed, the mixture is put into an oven for reaction for 2 to 4 hours to ensure that the crystal grows uniformly, the reaction temperature is 120 ℃ and 180 ℃, the grain size is controlled between 70 nm and 160nm, the mixture is naturally cooled to the room temperature, and the white product can be obtained after centrifugation. The second step is that: washing the product with deionized water until the waste liquid is neutral, then placing the product in an oven to dry at 30-100 ℃, dropwise adding absolute ethyl alcohol into the product before drying, wherein the drying temperature is 30-100 ℃, and finally grinding the product for 30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
3) hot-press molding of the microporous nanocrystalline: and (3) placing the treated nanocrystalline powder into a designed mold, and molding by using a vacuum hot-pressing technology, wherein the hot-pressing temperature is controlled within the range of 100-600 ℃, and the pressure is controlled within the range of 20-70 MPa.
Has the advantages that: the synthesis method of the microporous nanocrystal is simple and controllable, and has lower reaction temperature and short reaction time. The invention can effectively complete micropore control and uniform growth of the micropore nanocrystalline, and the room temperature ionic conductivity and chemical stability of the micropore nanocrystalline are far superior to those of the traditional oxide crystal material.
Drawings
FIG. 1 is an X-ray diffraction chart of a crystal in example 1 of the present invention;
FIG. 2 is a TEM image in example 1 of the present invention;
FIG. 3 is a schematic diagram of the sodium ion channel in different directions in example 1 of the present invention.
Detailed Description
The particle size of the solid ionic electrolyte is 50-300nm, and after the microporous nanocrystal powder is subjected to hot press molding, an electrical property test is directly carried out.
Example 1
Preparing a microporous nanocrystalline miscible substance: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, adding into a small beaker, adding 6ml of concentrated phosphoric acid and 24ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: firstly, adding 10-15ml of absolute ethyl alcohol into a big beaker, then dropwise adding weighed 2mmol of tetrabutyl titanate, uniformly stirring by using a magnetic stirrer, and continuously adding absolute ethyl alcohol to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 5min after the dropwise addition is finished; and obtaining the microporous nanocrystalline miscible liquid preparation.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution of the miscible substances, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven for reacting for 3 hours at 160 ℃ to ensure that crystals grow uniformly, naturally cooling the reaction kettle to room temperature, and centrifuging the reaction kettle to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 60 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 100 ℃, and the pressure is controlled within 20 MPa.
The crystal form is determined to be orthorhombic NaTi by testing2(PO4)3The conductivity can reach 2.594 x 10 when tested under the condition of room temperature-4S·cm-1。
According to the International Union of Pure and Applied Chemistry (IUPAC) regulations, mesoporous materials refer to a class of porous materials with pore sizes between 2-50nm, and porous materials with pore sizes less than 2nm are called Microporous materials (microporosius materials).
According to a TEM image (bright spots are holes of the material) and a crystal X-ray diffraction pattern, the prepared material has the hole diameter below 2nm and belongs to a microporous crystal material.
Example 2
Preparing a microporous nanocrystalline miscible substance: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, putting the sodium acetate trihydrate into a small beaker, adding 6ml of concentrated phosphoric acid and 24ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: firstly, 10ml of absolute ethyl alcohol is added into a big beaker, then 2mmol of weighed tetrabutyl titanate is added dropwise, a magnetic stirrer is used for stirring uniformly, and the absolute ethyl alcohol is continuously added to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 6min after the dropwise addition is finished; and obtaining the microporous nanocrystalline miscible liquid preparation.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven at 145 ℃ for 4 hours to ensure that crystals grow uniformly, controlling the size of crystal grains to be between 70 and 160nm, naturally cooling the mixture to room temperature, and centrifuging the mixture to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 100 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 100 ℃, and the pressure is controlled within 20 MPa.
The test determines that the precipitated crystal is orthorhombic NaTi2(PO4)3The conductivity can reach 5.836 multiplied by 10 when tested under the condition of room temperature-4S·cm-1。
Example 3
Preparing a microporous nanocrystalline miscible substance: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, putting the sodium acetate trihydrate into a small beaker, adding 6ml of concentrated phosphoric acid and 24ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: adding 15ml of absolute ethyl alcohol into a large beaker, then dropwise adding weighed 2mmol of tetrabutyl titanate, uniformly stirring by using a magnetic stirrer, and continuously adding the absolute ethyl alcohol to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 5min after the dropwise addition is finished; and obtaining the mixed solution of the microporous nanocrystal.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution of the miscible substances, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven for 4 hours at 140 ℃ to ensure that crystals grow uniformly, controlling the size of crystal grains to be between 70 and 160nm, naturally cooling the mixture to room temperature, and centrifuging the mixture to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 90 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 100 ℃, and the pressure is controlled within 20 MPa.
The test confirms that the precipitated crystal is the NaTi with an orthorhombic crystal form2(PO4)3The conductivity can reach 1.061 multiplied by 10 when tested under the condition of room temperature-3S·cm-1。
Example 4
Preparing a microporous nanocrystal sodium ion electrolysis mother solution: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, putting the sodium acetate trihydrate into a small beaker, adding 6ml of concentrated phosphoric acid and 35ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: firstly, 10ml of absolute ethyl alcohol is added into a big beaker, then 2mmol of weighed tetrabutyl titanate is added dropwise, a magnetic stirrer is used for stirring uniformly, and the absolute ethyl alcohol is continuously added to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 6min after the dropwise addition is finished; and obtaining the mixed solution of the microporous nanocrystal.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven to react for 2.5 hours at the temperature of 120 ℃ to ensure that crystals grow uniformly, controlling the size of crystal grains to be between 70 and 160nm, naturally cooling the crystal grains to the room temperature, and centrifuging the crystal grains to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 80 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 100 ℃, and the pressure is controlled within 30 MPa.
The test confirms that the precipitated crystal is the NaTi with an orthorhombic crystal form2(PO4)3The conductivity can reach 5.093 x 10 when tested under the condition of room temperature-4S·cm-1。
Example 5
Preparing a microporous nanocrystal sodium ion electrolysis mother solution: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, putting the sodium acetate trihydrate into a small beaker, adding 6ml of concentrated phosphoric acid and 35ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: firstly, 10ml of absolute ethyl alcohol is added into a big beaker, then 2mmol of weighed tetrabutyl titanate is added dropwise, a magnetic stirrer is used for stirring uniformly, and the absolute ethyl alcohol is continuously added to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 8min after the dropwise addition is finished; and obtaining the mixed solution of the microporous nanocrystal.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven for 8 hours at 200 ℃ to ensure that crystals grow uniformly, controlling the size of crystal grains to be between 70 and 160nm, naturally cooling the mixture to room temperature, and centrifuging the mixture to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 80 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 600 ℃, the pressure is controlled within 70MPa, and the time is 0.5 h.
The test confirms that the precipitated crystal is the NaTi with an orthorhombic crystal form2(PO4)3The conductivity can reach 6.598 x 10 when tested under the condition of room temperature-5S·cm-1。
Example 6
Preparing a microporous nanocrystal sodium ion electrolysis mother solution: the first step is as follows: weighing 2mmol of sodium acetate trihydrate, putting the sodium acetate trihydrate into a small beaker, adding 6ml of concentrated phosphoric acid and 35ml of absolute ethyl alcohol, and carrying out ultrasonic treatment until the sodium acetate is completely dissolved. The second step is that: firstly, 10ml of absolute ethyl alcohol is added into a big beaker, then 2mmol of weighed tetrabutyl titanate is added dropwise, a magnetic stirrer is used for stirring uniformly, and the absolute ethyl alcohol is continuously added to a constant volume of 60 ml. The third step: and uniformly stirring the mixed solution in the small beaker, dropwise adding the mixed solution into the large beaker which is continuously stirred, continuously increasing the stirring speed according to the change of the solution color from clear to opaque in the dropwise adding process, and properly reducing the stirring speed to continue stirring after the color is lightened. If the stirring time is too long, a small amount of precipitate is produced, so the stirring is generally carried out for 6min after the dropwise addition is finished; and obtaining the mixed solution of the microporous nanocrystal.
Crystallization treatment of microporous nanocrystalline sodium ion electrolyte: the first step is as follows: uniformly mixing the mixed solution of the miscible substances, uniformly dividing the mixed solution into two parts, putting the two parts into a reaction kettle with the capacity of 100ml of polytetrafluoroethylene material, screwing a cover, putting the reaction kettle into an oven for reaction at 120 ℃ for 2 hours to ensure that crystals grow uniformly, controlling the size of crystal grains to be between 70 and 160nm, naturally cooling the mixture to room temperature, and centrifuging the mixture to obtain a wet white product. The second step is that: washing the product with deionized water until the waste liquid becomes neutral, then placing the product in an oven for drying at 80 ℃, and finally grinding the product for 10-30min by using an agate mortar to obtain titanium sodium phosphate nanocrystalline powder;
hot-press molding of the microporous nanocrystalline: and (3) putting the treated nanocrystalline powder into a designed die, and forming by using a vacuum hot pressing technology, wherein the hot pressing temperature is controlled within 100 ℃, the pressure is controlled within 20MPa, and the time is 3 h.
The test confirms that the precipitated crystal is the NaTi with an orthorhombic crystal form2(PO4)3The conductivity can reach 5.093 x 10 when tested under the condition of room temperature-4S·cm-1。
Claims (2)
1. A preparation method of a microporous nanocrystalline sodium ion solid electrolyte is characterized by comprising the following steps:
preparation of the electrolyteThe material mole percentage is: 20-60% of phosphoric acid, 10-30% of titanium compound and 20-40% of sodium salt, wherein the sum of mole percentages is 100%; the phosphoric acid is 85 wt% of H3PO4(ii) a The titanium compound is selected from one or a mixture of more of tetrabutyl titanate, titanium tetrachloride and barium titanate; the sodium salt is selected from one or more of sodium acetate, sodium phosphate, disodium hydrogen phosphate, sodium acetate and sodium carbonate;
the preparation method comprises the following steps:
1) preparing a microporous nanocrystalline miscible substance: dissolving sodium salt and concentrated phosphoric acid in an organic solvent to obtain a mixed solution A; dissolving a titanium compound in an organic solvent to obtain a titanium compound organic solution, dropwise adding the mixed solution A into the titanium compound organic solution, and stirring for 5-8min after dropwise adding to obtain a microporous nanocrystal miscible substance preparation solution;
2) crystallization treatment of microporous nanocrystalline sodium ion electrolyte: sealing the mixed solution in a reaction kettle, reacting the reaction kettle at the temperature of 120-200 ℃ for 2-8h to ensure that crystals grow uniformly, controlling the size of crystal grains to be 50-300nm, washing and drying to obtain the titanium sodium phosphate microporous nanocrystalline;
3) hot-press molding of the microporous nanocrystalline: adding the sodium titanium phosphate microporous nanocrystalline powder into a designed mold, molding by using a vacuum hot-pressing technology, and controlling the hot-pressing temperature within the range of 100-600 ℃, the pressure within the range of 20-70MPa and the time within 0.5-3 h.
2. The method for preparing a microporous nanocrystalline sodium ion solid state electrolyte according to claim 1, wherein: in the dropping process in the step 1), the stirring speed is continuously increased according to the change of the color of the miscible substance from clear to opaque; when the color of the solution becomes light, the stirring speed is properly reduced to continue stirring.
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| CN105742727A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院物理研究所 | Secondary battery, application and preparation method of negative electrode of secondary battery |
| CN105810912A (en) * | 2016-05-10 | 2016-07-27 | 武汉理工大学 | Three-dimensional graded carbon-clad NaTi<2>(PO<4>)<3>/C micrometer flower electrode material and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939864A (en) * | 2008-02-04 | 2011-01-05 | 住友化学株式会社 | Powder for positive electrode active material, positive electrode active material, and sodium rechargeable battery |
| JP2016050154A (en) * | 2014-09-01 | 2016-04-11 | 株式会社オハラ | Glass ceramic |
| CN105742727A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院物理研究所 | Secondary battery, application and preparation method of negative electrode of secondary battery |
| CN105810912A (en) * | 2016-05-10 | 2016-07-27 | 武汉理工大学 | Three-dimensional graded carbon-clad NaTi<2>(PO<4>)<3>/C micrometer flower electrode material and preparation method and application thereof |
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