CN112786857B - Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof - Google Patents

Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof Download PDF

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CN112786857B
CN112786857B CN202110066435.6A CN202110066435A CN112786857B CN 112786857 B CN112786857 B CN 112786857B CN 202110066435 A CN202110066435 A CN 202110066435A CN 112786857 B CN112786857 B CN 112786857B
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manganese
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CN112786857A (en
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刘杰飞
侯贤华
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South China Normal University
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Abstract

The invention discloses a fast ion conductor sodium secondary battery anode material and a preparation method and application thereof. The preparation method comprises the following steps: (1) weighing a sodium source, a manganese source, a titanium source, a phosphorus source and an organic ligand according to a stoichiometric ratio, adding the sodium source, the manganese source, the titanium source, the phosphorus source and the organic ligand into a solvent, stirring and dissolving the mixture, heating and stirring the mixture under a water bath condition of 60-90 ℃ until the water is completely volatilized, drying the mixture, grinding the mixture into powder to obtain a gel precursor Na3+2xMn1+xTi1‑x(PO4)3(ii) a Wherein x is more than or equal to 0.15 and less than or equal to 0.3; (2) and calcining the obtained gel precursor in a protective gas atmosphere at 600-700 ℃, and obtaining the fast ion conductor sodium secondary battery anode material after the calcination is finished. The anode material prepared by the invention has high energy density, excellent cycle performance, good rate performance and high first coulombic efficiency, and can be used in the field of sodium secondary batteries.

Description

Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of new energy, in particular to a fast ion conductor sodium secondary battery positive electrode material and a preparation method and application thereof.
Background
The advantages of high energy density, long service life and no memory effect enable the lithium secondary battery to be widely applied to 3C electronic products, portable electronic devices and electric vehicles, but the lithium secondary battery is limited by limited lithium resources and increasing cost, and is difficult to meet the requirements of future large-scale energy storage and low energy density application scenarios. Sodium is abundant in reserve, wide in distribution, simple to prepare, low in price and environment-friendly, so that the sodium can be used as a next-generation battery to meet the requirement of large-scale energy storage. Development of high-performance, long-life, low-cost secondary batteries has become a current research focus.
The phosphate fast ion conductor (NASICON) material has three-dimensional sodium ion transmission channels, a stable structure, high thermal stability and low water and oxygen sensitivity, and is a sodium secondary battery cathode material with great potential. But the relatively low theoretical specific capacity of the phosphate fast ion conductor material is usually 100-120 mAh g due to large molecular weight-1And poor electron conductivity due to the strong induction effect of phosphate. Meanwhile, vanadium metal in the center of the phosphate fast ion conductor material is generally toxic, low in storage capacity and high in cost. These disadvantages of phosphate fast ion conductor type materials have seriously hindered its application and development in the field of sodium secondary batteries.
The non-toxic and low-cost metal is used for partially replacing vanadium or developing a vanadium-free fast ion conductor type positive electrode material, so that the preparation cost can be reduced, the aim of pollution-free green process can be fulfilled, and the aim can be successfully fulfilled by discovering the manganese-based phosphate fast ion conductor type positive electrode material. Especially Na3MnTi(PO4)3Not only does not contain toxic and expensive central metal, but also Mn and Ti in the material can participate in the reaction, so that the multi-electron reaction of the material can realize more than 150mAh g-1The energy density of the material can exceed 400Wh/kg at the material level, which is higher than that of the reported most fast ionic conductor type sodium electric anode materials. But its sodium-deficient structure results in its lower first effect and where the reaction potential of Ti is only 2.1V, the overall energy density of the material will be low. Therefore, it is of great importance to provide an electrode material having a high energy density and first coulombic efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a positive electrode material of a fast ion conductor sodium secondary battery.
The invention also aims to provide the positive electrode material of the fast ion conductor sodium secondary battery prepared by the method.
The invention also aims to provide application of the positive electrode material of the fast ion conductor sodium secondary battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a fast ion conductor sodium secondary battery anode material comprises the following steps:
(1) preparation of gel precursor Na3+2xMn1+xTi1-x(PO4)3
Weighing a sodium source, a manganese source, a titanium source, a phosphorus source and an organic ligand (carbon source) according to a stoichiometric ratio, adding the sodium source, the manganese source, the titanium source, the phosphorus source and the organic ligand (carbon source) into a solvent, stirring and dissolving the mixture, heating and stirring the mixture under a water bath condition of 60-90 ℃ until water is completely volatilized, drying the mixture, grinding the mixture into powder to obtain a gel precursor Na3+2xMn1+xTi1-x(PO4)3(ii) a Wherein x is more than or equal to 0.15 and less than or equal to 0.3;
(2) preparation of Na3+2xMn1+xTi1-x(PO4)3C material
Subjecting the gel precursor Na obtained in the step (1) to3+2xMn1+xTi1-x(PO4)3Calcining at 600-700 ℃ in a protective gas atmosphere to obtain Na after the calcination is finished3+2xMn1+xTi1-x(PO4)3the/C material is the positive electrode material of the fast ion conductor sodium secondary battery.
The value range of x in the step (1) is preferably as follows: x is more than or equal to 0.15 and less than or equal to 0.2.
The sodium source in the step (1) is a soluble sodium source; preferably one or more of sodium acetate, sodium formate, sodium oxalate, sodium gluconate, sodium citrate, sodium nitrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium ammonium hydrogen phosphate and trisodium phosphate; more preferably at least one of sodium acetate and sodium dihydrogen phosphate.
The manganese source in the step (1) is a soluble manganese source; preferably one or more of manganese acetate, manganese nitrate and manganese dihydrogen phosphate; more preferably manganese acetate tetrahydrate.
The titanium source in the step (1) is a soluble titanium source; preferably one or more of tetraethyl titanate, titanium isooctanolate, titanium tetramethoxide, tetrabutyl titanate, bis (acetylacetonyl) diisopropyl titanate, isopropyl titanate and bis (2-hydroxypropionic acid) diammonium dihydroxide titanium; more preferably at least one of titanium bis (2-hydroxypropionate) dihydroxide and isopropyl titanate; the titanium source can be prepared into solution by adding water and then mixed with other substances.
The phosphorus source in the step (1) is at least one of phosphoric acid and phosphate; preferably one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium ammonium hydrogen phosphate; more preferably one or more of diammonium phosphate, sodium dihydrogen phosphate and phosphoric acid.
The molar ratio of the sum of manganese element in the manganese source and titanium element (transition metal element) in the titanium source to phosphorus element in the phosphorus source in the step (1) is 1: 1.5.
the organic ligand (carbon source) in the step (1) is one or more of citric acid, glucose, sucrose, amino acid, glycine, L-leucine and water-soluble starch; preferably one or more of citric acid, glucose and sucrose.
The molar ratio of the sum of manganese element in the manganese source and titanium element (i.e. transition metal element) in the titanium source to the organic ligand (carbon source) in the step (1) is 1:1 to 1.5.
The solvent in the step (1) is at least one of water and ethanol.
The water is preferably deionized water.
The dosage of the solvent in the step (1) is calculated according to the proportion of 20-30 ml of solvent per millimole of sodium source; preferably, the amount of the solvent is 25-30 ml per millimole of the sodium source.
The gel precursor Na in the step (1)3+2xMn1+xTi1-x(PO4)3The molar ratio of the medium Na element, the Mn element and the Ti element is 3.3-3.5: 1.15-1.3: 0.7 to 0.85; preferably 3.3-3.4: 1.15-1.2: 0.8 to 0.85.
The gel precursor Na in the step (1)3+2xMn1+xTi1-x(PO4)3Preferably Na3.4Mn1.2Ti0.8(PO4)3、Na3.3Mn1.15Ti0.85(PO4)3And Na3.6Mn1.3Ti0.7(PO4)3At least one of; more preferably Na3.4Mn1.2Ti0.8(PO4)3And Na3.3Mn1.15Ti0.85(PO4)3At least one of (1).
The temperature of the water bath conditions described in step (1) is preferably 80 ℃.
The drying described in step (1) is preferably carried out in a forced air drying oven.
The drying temperature in the step (1) is 100-200 ℃; preferably 110 deg.c.
The drying time in the step (1) is 3-12 h; preferably 10-12 h; more preferably 10 h.
The protective gas in the step (2) is nitrogen or argon, and the flow rate of the protective gas is 0.3-0.6 ml/s.
The temperature of the calcination in the step (2) is preferably 650 ℃.
The calcining time in the step (2) is 4-24 hours; preferably 12-24 h; more preferably 12 h.
A fast ion conductor sodium secondary battery cathode material is prepared by any one of the methods.
The fast ion conductor sodium secondary battery anode material is applied to the battery field.
The battery is a secondary battery, such as a sodium secondary battery and the like.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention provides a novel Na-coated manganese-rich, sodium-rich and carbon-coated Na3+2xMn1+xTi1-x(PO4)3a/C (0.15 x 0.3; preferably 0.15 x 0.2) fast ion conductor type high energy density sodium electric anode material, Na prepared by increasing the content of sodium and manganese in the material3+2xMn1+xTi1-x(PO4)3sodium/C electric anode materialThe composition ratio of the elements Na, Mn and Ti is adjustable, and electrochemical test results show that when the manganese content is increased by 0.15 to 0.2, the energy density and the rate capability of the material are obviously improved for the first time, and the energy density of the material is reduced when the manganese content is continuously increased. The anode material has high energy density, excellent cycle performance, good rate performance and high first coulombic efficiency.
(2) According to the invention, the initial structure sodium content is increased, and the low-potential titanium is replaced by the high-potential metal, so that the energy density of the material can be improved, and the first effect of the material can be improved, and the material can meet the actual use requirement.
(3) The method is simple, the process flow is simple, the used solvent and raw materials can adopt cheap, nontoxic and pollution-free products, and the method has the advantages of high cost and environmental protection.
(4) Because the energy density of the battery material is difficult to improve, and particularly when a material system has no great breakthrough, the conventional optimization is only to improve the service life and the rate capability, and the positive electrode material Na in the invention3+2xMn1+xTi1-x(PO4)3C and existing Na3MnTi(PO4)3Compared with the prior art, the method has the following characteristics: the material theoretically raises the voltage of the material so as to raise the energy density; the material improves the first coulombic efficiency, and the improvement of the first coulombic efficiency is beneficial to the improvement of the energy density of the battery; ③ energy density of the material is compared with Na3MnTi(PO4)3Increasing by 33-40 Wh/kg.
Drawings
FIG. 1 shows Na prepared in example 13.4Mn1.2Ti0.8(PO4)3Scanning electron microscopy images of (a); wherein A is amplified by 1000 times; b is 10000 times magnification.
FIG. 2 shows Na prepared in examples 1 to 33.4Mn1.2Ti0.8(PO4)3/C、Na3.3Mn1.15Ti0.85(PO4)3/C、Na3.6Mn1.3Ti0.7(PO4)3Powder sample of/C and Na prepared in comparative example3MnTi(PO4)3X-ray diffraction pattern of/C powder samples.
FIG. 3 shows Na prepared in example 13.4Mn1.2Ti0.8(PO4)3Charge-discharge curve of/C in sodium secondary battery.
FIG. 4 shows Na prepared in example 13.4Mn1.2Ti0.8(PO4)3Graph of cycle performance of/C in sodium secondary battery.
FIG. 5 shows Na prepared in example 23.3Mn1.15Ti0.85(PO4)3Charge-discharge curve of/C in sodium secondary battery.
FIG. 6 shows Na prepared in example 23.3Mn1.15Ti0.85(PO4)3Graph of cycle performance of/C in sodium secondary battery.
FIG. 7 shows Na prepared in example 33.6Mn1.3Ti0.7(PO4)3Charge-discharge curve of/C in sodium secondary battery.
FIG. 8 shows Na prepared in example 33.6Mn1.3Ti0.7(PO4)3Graph of cycle performance of/C in sodium secondary battery.
FIG. 9 shows Na prepared in comparative example3MnTi(PO4)3Graph of cycle performance of/C in sodium secondary battery.
FIG. 10 shows Na prepared in examples 1 to 3 and comparative example3MnTi(PO4)3/C、Na3.3Mn1.15Ti0.85(PO4)3/C、Na3.4Mn1.2Ti0.8(PO4)3/C、Na3.6Mn1.3Ti0.7(PO4)3Energy density per C versus graph.
FIG. 11 shows Na prepared in examples 1 to 3 and comparative example3MnTi(PO4)3/C、Na3.3Mn1.15Ti0.85(PO4)3/C、Na3.4Mn1.2Ti0.8(PO4)3/C、Na3.6Mn1.3Ti0.7(PO4)3Average discharge voltage per C versus graph.
FIG. 12 shows Na prepared in examples 1 to 3 and comparative example3MnTi(PO4)3/C、Na3.3Mn1.15Ti0.85(PO4)3/C、Na3.4Mn1.2Ti0.8(PO4)3/C、Na3.6Mn1.3Ti0.7(PO4)3First coulombic efficiency comparison plot.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
The purity of the raw materials such as organic ligand (namely carbon source), manganese source, sodium source, phosphorus source and the like is more than or equal to 85 percent (preferably more than or equal to 95 percent, and more preferably more than or equal to 99 percent); the glucose monohydrate and the sucrose referred to in the examples are Analytical Reagents (AR), and the purity of the citric acid monohydrate is 99.8%; the purity of the manganese acetate tetrahydrate is 99 percent; the purity of the anhydrous sodium acetate is 99.99 percent; the purity of ammonium dihydrogen phosphate and sodium dihydrogen phosphate is 99 percent, and the purity of phosphoric acid is 85 percent; the purity of isopropyl titanate was 95%.
Example 1
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
weighing 0.505g of citric acid monohydrate, 0.237g of manganese acetate tetrahydrate, 0.376g of a solution (50 mass percent of aqueous solution) of titanium dihydroxide diammonium di (2-hydroxypropionate), 0.223g of anhydrous sodium acetate and 0.278g of ammonium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, and then grinding the sample into powderObtaining Na3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
putting the obtained gel precursor powder into an alumina porcelain boat, then putting the alumina porcelain boat into a tube furnace, introducing argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing:
preparing Na3.4Mn1.2Ti0.8(PO4)3The material was observed under a scanning electron microscope, and the results are shown in FIG. 1.
② Na prepared by the above method3.4Mn1.2Ti0.8(PO4)3The material was subjected to x-ray diffraction analysis and the results are shown in figure 2.
Testing electrochemical performance: using Na prepared as described above3.4Mn1.2Ti0.8(PO4)3Mixing and pulping the materials with a conductive agent (SP), a binder (polyvinylidene fluoride (PVDF)) and an N-methylpyrrolidone (NMP) dispersing agent (the mass ratio is 7: 2: 1: 50), and taking the obtained electrode plate as the positive electrode of the sodium-ion battery; sodium sheet as counter electrode, NaClO4Adding into mixed solution of EC (ethylene carbonate) and DMC (dimethyl carbonate) with the volume ratio of EC and DMC of 1:1 to obtain 1mol/L NaClO4The solution is used as electrolyte and assembled into a sodium ion half cell for testing.
Na3.4Mn1.2Ti0.8(PO4)3The charge-discharge curve of the material in the sodium secondary battery is shown in fig. 3, the cycle performance is shown in fig. 4, the energy density is shown in fig. 10, the average discharge voltage is shown in fig. 11, and the first coulombic efficiency is shown in fig. 12. In a voltage range of 1.5-4.3V and under a current density of 15mA/g, the material shows a specific capacity of 151mAh/g, and the first coulombic efficiency is 88.6%. At a current density of 150mA/gAfter 500 weeks of the next cycle, the capacity retention was 86.6% and the material energy density was 475.6Wh/kg (energy density obtained from the battery test system test).
Example 2
(1)Na3.3Mn1.15Ti0.85(PO4)3Preparation of a gel precursor:
weighing 0.505g of citric acid monohydrate, 0.227g of manganese acetate tetrahydrate, 0.400g of a solution (50 mass percent of aqueous solution) of titanium dihydroxide and bis (2-hydroxypropionic acid) diammonium hydrogen oxide, 0.216g of anhydrous sodium acetate and 0.278g of ammonium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, then grinding the sample into powder to obtain Na3.3Mn1.15Ti0.85(PO4)3And (5) gel precursor.
(2)Na3.3Mn1.15Ti0.85(PO4)3Preparation of/C:
transferring the obtained gel precursor powder into an alumina porcelain boat, then placing the alumina porcelain boat in a tube furnace, introducing continuous argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.3Mn1.15Ti0.85(PO4)3a/C powder sample.
(3) And (3) performance testing: the x-ray diffraction analysis and electrochemical performance testing were the same as in example 1.
Na3.3Mn1.15Ti0.85(PO4)3The x-ray diffraction pattern of (a) is shown in fig. 2, the charge-discharge curve in the sodium secondary battery is shown in fig. 5, the cycle performance curve is shown in fig. 6, the energy density is shown in fig. 10, the average discharge voltage is shown in fig. 11, and the first coulombic efficiency is shown in fig. 12. Na (Na)3.3Mn1.15Ti0.85(PO4)3The capacity of 161mAh/g is shown in a sodium secondary battery, and the first coulombic efficiency is 79.4%. After 500 weeks cycling at a current density of 150mA/g, the capacity retention was 87.4% and the material energy density was 484.5 Wh/kg.
Example 3
(1)Na3.6Mn1.3Ti0.7(PO4)3Preparation of a gel precursor:
weighing 0.505g of citric acid monohydrate, 0.257g of manganese acetate tetrahydrate, 0.329g of a solution (50 mass percent of aqueous solution) of titanium dihydroxide diammonium di (2-hydroxypropionate), 0.236g of anhydrous sodium acetate and 0.278g of ammonium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, then grinding the sample into powder to obtain Na3.6Mn1.3Ti0.7(PO4)3And (5) gel precursor.
(2)Na3.6Mn1.3Ti0.7(PO4)3Preparation of/C:
transferring the obtained gel precursor powder into an alumina porcelain boat, then placing the alumina porcelain boat in a tube furnace, introducing continuous argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.6Mn1.3Ti0.7(PO4)3a/C powder sample.
(3) And (3) performance testing: the x-ray diffraction analysis and electrochemical performance testing were the same as in example 1.
Na3.6Mn1.3Ti0.7(PO4)3The x-ray diffraction pattern of (a) is shown in fig. 2, the charge-discharge curve in the sodium secondary battery is shown in fig. 7, the cycle performance curve is shown in fig. 8, the energy density is shown in fig. 10, the average discharge voltage is shown in fig. 11, and the first coulombic efficiency is shown in fig. 12. Na (Na)3.6Mn1.3Ti0.7(PO4)3The capacity of 122.5mAh/g is shown in a sodium secondary battery, and the first coulombic efficiency is 98%. After 500 weeks cycling at a current density of 150mA/g, the capacity retention was 66% and the material energy density was 391.7 Wh/kg.
Example 4
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
weighing 0.336g of citric acid monohydrate, 0.237g of manganese acetate tetrahydrate, 0.376g of a solution (50 mass percent of aqueous solution) of titanium dihydroxide and bis (2-hydroxypropionic acid), 0.223g of anhydrous sodium acetate and 0.278g of ammonium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, then grinding the sample into powder to obtain Na3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
transferring the obtained gel precursor powder into an alumina porcelain boat, then placing the alumina porcelain boat in a tube furnace, introducing continuous argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3.4Mn1.2Ti0.8(PO4)3A capacity of about 156mAh/g was exhibited in the sodium secondary battery, and the material energy density was 479.5 Wh/kg.
Example 5
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
citric acid monohydrate 0.505g, manganese acetate tetrahydrate 0.237g, sodium acetate anhydrous 0.223g, ammonium dihydrogen phosphate 0.278g were weighed into a 100ml beaker, 40ml of deionized water was added and stirred until the sample dissolved, as solution a. A further 0.191g of isopropyl titanate are weighed out into 30ml of pure ethanol as solution B. Solution B was added to solution A by a peristaltic pump at a rate of 0.5 ml/min. Transferring the obtained solution into 80 deg.C water bath, stirring and heating until water is completely volatilized, drying the obtained sample in 110 deg.C forced air drying oven for 10 hr, and grinding the sample into powderFinally, Na is obtained3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
transferring the obtained gel precursor powder into an alumina porcelain boat, then placing the alumina porcelain boat in a tube furnace, introducing continuous argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3.4Mn1.2Ti0.8(PO4)3A capacity of about 159mAh/g was exhibited in the sodium secondary battery, and the material energy density was 483.2 Wh/kg.
Example 6
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
weighing 0.505g of citric acid monohydrate, 0.237g of manganese acetate tetrahydrate, 0.376g of a solution (50 mass percent of aqueous solution) of titanium dihydroxide di (2-hydroxypropionic acid) and diammonium dihydroxide, 0.026g of anhydrous sodium acetate and 0.291g of anhydrous sodium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a blast drying oven at 110 ℃ for 10 hours, and then grinding the sample into powder to obtain Na3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
transferring the obtained gel precursor powder into an alumina porcelain boat, then placing the alumina porcelain boat in a tube furnace, introducing continuous argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3.4Mn1.2Ti0.8(PO4)3A capacity of about 153mAh/g was exhibited in the sodium secondary battery, and the material energy density was 478.3 Wh/kg.
Example 7
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
weighing 0.485g of monohydrate dextrose, (AR), 0.237g of tetrahydrate manganese acetate, 0.376g of a solution (50 mass percent of aqueous solution) of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium, 0.223g of anhydrous sodium acetate and 0.277g of phosphoric acid in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized and dried, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, and then grinding the sample into powder to obtain Na3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
putting the obtained gel precursor powder into an alumina porcelain boat, then putting the alumina porcelain boat into a tube furnace, introducing argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3.4Mn1.2Ti0.8(PO4)3A specific capacity of about 156mAh/g was exhibited in the sodium secondary battery, and the material energy density was 482.5 Wh/kg.
Example 8
(1)Na3.4Mn1.2Ti0.8(PO4)3Preparation of a gel precursor:
sucrose (0.822 g), (AR), manganese acetate tetrahydrate (0.237 g), bis (2-hydroxypropionic acid) were weighed out)0.376g of diammonium dihydroxide titanium solution (aqueous solution with the mass fraction of 50%), 0.223g of anhydrous sodium acetate and 0.277g of phosphoric acid are put into a 100ml beaker, 70ml of deionized water is added and stirred until the sample is dissolved, the beaker is transferred into a 80 ℃ water bath kettle to be stirred and heated until the water is completely volatilized, the obtained sample is dried for 10 hours in a 110 ℃ forced air drying oven, then the sample is ground into powder to obtain Na3.4Mn1.2Ti0.8(PO4)3And (5) gel precursor.
(2)Na3.4Mn1.2Ti0.8(PO4)3Preparation of/C:
putting the obtained gel precursor powder into an alumina porcelain boat, then putting the alumina porcelain boat into a tube furnace, introducing argon flow (0.3-0.6 ml/s), calcining the gel precursor powder for 12 hours at the temperature of 650 ℃, and cooling the gel precursor powder to room temperature to obtain Na3.4Mn1.2Ti0.8(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3.4Mn1.2Ti0.8(PO4)3A specific capacity of about 152mAh/g was exhibited in the sodium secondary battery, and the material energy density was 477.2 Wh/kg.
Comparative examples
(1)Na3MnTi(PO4)3Preparation of a gel precursor:
weighing 0.505g of citric acid monohydrate, 0.198g of manganese acetate tetrahydrate, 0.470g of a solution (50% by mass of aqueous solution) of titanium dihydroxide di (2-hydroxypropionic acid) and titanium, 0.197g of anhydrous sodium acetate and 0.278g of ammonium dihydrogen phosphate in a 100ml beaker, adding 70ml of deionized water, stirring until the sample is dissolved, transferring the beaker into a water bath kettle at 80 ℃, stirring and heating until the water is completely volatilized, drying the obtained sample in a 110 ℃ forced air drying oven for 10 hours, then grinding the sample into powder to obtain Na3MnTi(PO4)3And (5) gel precursor.
(2)Na3MnTi(PO4)3Preparation of/C:
placing the obtained gel precursor powder in aluminaPlacing the porcelain boat in a tube furnace, introducing argon flow (0.3-0.6 ml/s), calcining at 650 ℃ for 12h, and cooling to room temperature to obtain Na3MnTi(PO4)3a/C powder sample.
(3) And (3) performance testing: electrochemical performance was tested as in example 1.
Na3MnTi(PO4)3The cycle performance curve in the sodium secondary battery is shown in fig. 9, the energy density is shown in fig. 10, the average discharge voltage is shown in fig. 11, and the first coulomb efficiency is shown in fig. 12. Na (Na)3MnTi(PO4)3A specific capacity of about 160mAh/g was exhibited in the sodium secondary battery. The first coulombic efficiency is 69.8 percent and is 150mA g-1The capacity retention rate is 87 percent after the current density is cycled for 500 weeks, and the energy density of the material is 442.4Wh kg-1。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a fast ion conductor sodium secondary battery anode material is characterized by comprising the following steps:
(1) preparation of gel precursor Na3+2xMn1+xTi1-x(PO4)3
Weighing a sodium source, a manganese source, a titanium source, a phosphorus source and an organic ligand according to a stoichiometric ratio, adding the sodium source, the manganese source, the titanium source, the phosphorus source and the organic ligand into a solvent, stirring and dissolving the mixture, heating and stirring the mixture under a water bath condition of 60-90 ℃ until the water is completely volatilized, drying the mixture, grinding the mixture into powder to obtain a gel precursor Na3+2xMn1+xTi1-x(PO4)3(ii) a Wherein x is more than or equal to 0.15 and less than or equal to 0.3;
(2) preparation of Na3+2xMn1+xTi1-x(PO4)3C material
Subjecting the gel precursor Na obtained in the step (1) to3+2xMn1+xTi1-x(PO4)3Calcining at 600-700 ℃ in a protective gas atmosphere to obtain Na after the calcination is finished3+2xMn1+xTi1-x(PO4)3the/C material is the positive electrode material of the fast ion conductor sodium secondary battery.
2. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 1, characterized in that:
the value range of x in the step (1) is as follows: x is more than or equal to 0.15 and less than or equal to 0.2.
3. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 1, characterized in that:
the sodium source in the step (1) is a soluble sodium source;
the manganese source in the step (1) is a soluble manganese source;
the titanium source in the step (1) is a soluble titanium source;
the phosphorus source in the step (1) is at least one of phosphoric acid and phosphate;
the organic ligand in the step (1) is one or more of citric acid, glucose, sucrose, amino acid, glycine, L-leucine and water-soluble starch.
4. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 3, characterized in that:
the sodium source in the step (1) is one or more of sodium acetate, sodium formate, sodium oxalate, sodium gluconate, sodium citrate, sodium nitrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium ammonium hydrogen phosphate and trisodium phosphate;
the manganese source in the step (1) is one or more of manganese acetate, manganese nitrate and manganese dihydrogen phosphate;
the titanium source in the step (1) is one or more of tetraethyl titanate, titanium isooctanoate, titanium tetramethoxide, tetrabutyl titanate, bis (acetylacetonato) diisopropyl titanate, isopropyl titanate and bis (2-hydroxypropionic acid) diammonium dihydroxide titanium;
the phosphorus source in the step (1) is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium ammonium hydrogen phosphate;
the organic ligand in the step (1) is one or more of citric acid, glucose and sucrose.
5. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 1, characterized in that:
the molar ratio of the sum of manganese element in the manganese source and titanium element in the titanium source to phosphorus element in the phosphorus source in the step (1) is 1: 1.5;
the molar ratio of the sum of manganese element in the manganese source and titanium element in the titanium source to the organic ligand in the step (1) is 1:1 to 1.5.
6. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 1, characterized in that:
the gel precursor Na in the step (1)3+2xMn1+xTi1-x(PO4)3The molar ratio of the medium Na element, the Mn element and the Ti element is 3.3-3.5: 1.15-1.3: 0.7 to 0.85;
the gel precursor Na in the step (1)3+2xMn1+xTi1-x(PO4)3Is Na3.4Mn1.2Ti0.8(PO4)3、Na3.3Mn1.15Ti0.85(PO4)3And Na3.6Mn1.3Ti0.7(PO4)3At least one of;
the dosage of the solvent in the step (1) is calculated according to the proportion of 20-30 ml of solvent per millimole of sodium source.
7. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 6, characterized in that:
step (ii) of(1) The gel precursor Na as described in (1)3+2xMn1+xTi1-x(PO4)3The molar ratio of the medium Na element to the Mn element to the Ti element is 3.3-3.4: 1.15-1.2: 0.8 to 0.85;
the gel precursor Na in the step (1)3+2xMn1+xTi1-x(PO4)3Is Na3.4Mn1.2Ti0.8(PO4)3And Na3.3Mn1.15Ti0.85(PO4)3At least one of (1).
8. The method for preparing the positive electrode material of the fast ion conductor sodium secondary battery according to claim 1, characterized in that:
the solvent in the step (1) is at least one of water and ethanol;
the temperature of the water bath condition in the step (1) is 80 ℃;
the drying in the step (1) is drying in a forced air drying oven;
the drying temperature in the step (1) is 100-200 ℃;
the drying time in the step (1) is 3-12 h;
the protective gas in the step (2) is nitrogen or argon, and the flow rate of the protective gas is 0.3-0.6 ml/s;
the calcining temperature in the step (2) is 650 ℃;
and (3) calcining for 4-24 hours in the step (2).
9. The positive electrode material of the fast ion conductor sodium secondary battery is characterized in that: prepared by the method of any one of claims 1 to 8.
10. The use of the fast ion conductor sodium secondary battery positive electrode material of claim 9 in the field of batteries.
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