CN116101994A - Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof - Google Patents

Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof Download PDF

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CN116101994A
CN116101994A CN202211584886.XA CN202211584886A CN116101994A CN 116101994 A CN116101994 A CN 116101994A CN 202211584886 A CN202211584886 A CN 202211584886A CN 116101994 A CN116101994 A CN 116101994A
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sodium
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positive electrode
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刘兴泉
徐林才
蔡淦
何泽珍
霍晋生
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University of Electronic Science and Technology of China
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
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    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract

The invention belongs to the technical field of sodium ion batteries, and particularly provides a heteropolyacid modified layered oxide sodium battery anode material and a preparation method thereof, which are used for solving the problems of the prior P2 type manganese-based layered oxide (P2-Na 2/3 MnO 2 ) There are a number of problems. According to the invention, the metal element (M) and the phosphorus (P) in the heteropoly acid are simultaneously introduced into the P2 type manganese-based layered oxide for doping modification for the first time, and the novel manganese-based layered oxide sodium ion battery anode material is prepared: P2-Na 2/3 Mn 1‑x (MP 1/12 ) x O 2 M= Mo, W, cr, V, x=0.001 to 0.3; the crystal phase structure of the material is a P2 type layered structure, the crystal system is a hexagonal crystal system,the space group is P63/mmc. The sodium ion battery anode material provided by the invention has the advantages of high initial discharge specific capacity, good cycle performance, long cycle life and the like; meanwhile, the positive electrode material of the sodium ion battery is prepared by a sol-gel method, has uniform particle size, good crystallization quality and high purity, is simple in process and easy to control, and can meet the requirements of large-scale industrial production.

Description

Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, relates to doping modification of a positive electrode material and preparation thereof, and particularly provides a novel manganese-based layered oxide sodium ion battery positive electrode material modified by doping heteropolyacid and a preparation method thereof, wherein the material has the following chemical formula: P2-Na 2/3 Mn 1-x (MP 1/12 ) x O 2 Wherein, M= Mo, W, cr, V, x=0.001-0.3, and P2-NMMPO is short for short.
Background
With the development of society, the demand for energy storage is increasing, and Lithium Ion Batteries (LIBs) dominate the portable electronic products and electric automobile markets; however, the lithium resource in China only accounts for 7% of the global resource, and the external dependence exceeds 60%, which is called white petroleum; and since 2021, lithium carbonate price was one femtoff (up to 60 ten thousand yuan/ton for 11/10/2022), lithium ore competition was increasingly underway; the scarcity of lithium resources and the rising price of lithium carbonate have made the development of alternative energy storage systems that utilize earth's abundant elements an urgent need. Sodium reserves on the earth are 420 times of lithium, and Sodium Ion Batteries (SIB) have the advantages of abundant sodium source reserves, low cost, high safety, excellent high and low temperature performance, compatibility with the existing lithium battery equipment, aluminum foil as current collectors, low sodium ion solvation energy, competitive energy density and the like, and are considered to be a very promising supplement to LIB; in a Sodium Ion Battery (SIB), a positive electrode material plays an important role in determining energy density, rate performance and cycle stability, and therefore, development of a novel positive electrode material to achieve excellent electrochemical performance of the SIB has an important meaning.
Currently, the positive electrode materials of sodium ion batteries can be mainly classified into three types: polyanion compound, prussian blue and transition metal oxide, and domestic sodium ion battery positive electrode material company are laid out on the three positive electrode materials, and positive promotion of sodium ion battery positive electrode material is achievedIndustrialization of materials. The polyanion compound is specifically Na x M y (XO 4 ) n X= S, P, m=fe, mn, and other transition metal elements; such as Na 3 V 2 (PO 4 ) 3 、NaVPO 4 F, the advantages of the device are stable structure, good cycle performance, high thermal stability and good safety performance; but also has the defects of larger relative molecular mass, lower energy density, poor electron conductivity and the like; the domestic layout enterprises include: penghui energy, shandong Champartment drum, etc. Prussian blue is specifically Na x Ma[M b (CN) 6 ] y M=fe, mn, etc.; its advantages are high energy density up to 160Wh/Kg; at the same time, the disadvantages are also obvious: poor conductivity, easy retention of crystal water, resulting in reduced specific capacity and cycle stability; furthermore, the presence of cyanide groups renders the material potentially toxic; in addition, the synthesis of the materials is difficult, and the large-scale preparation still needs to be further explored; the enterprises of the current layout have the Ningde times, starry sky sodium electricity and the like. The transition metal oxide is specifically Na x MeO 2 Me=fe, ni, mn, cu, etc.); the positive electrode material has the advantages of high specific capacity, rich reserves of transition metal elements, relatively simple synthesis process (solid phase method), compatibility with the existing lithium ion battery process, and is the most promising positive electrode material for the final industrialized application; it has a fatal disadvantage: poor stability and difficult synthesis; the enterprises in the current layout include Zhongkehaina, sodium and innovative energy sources.
In general, sodium-based layered oxide materials based on the order of sodium ion occupancy and oxygen stacking can be divided into four general categories: p2 type, P3 type, O2 type and O3 type, letters "P" and "O" respectively represent prismatic and octahedral coordination environments of Na ions, and numerals "2" and "3" respectively represent the number of transition metal layers in each repeating unit. It is widely believed that the P2 structured sodium intercalated oxide exhibits better electrochemical behavior than the O3 featured oxide due to its broad prismatic path within the TMO2 plate and direct diffusion of sodium ions. P2 type manganese-based layered oxide (Na x MnO 2 X is more than or equal to 0.5 and less than or equal to 0.8) is widely paid attention to due to simple synthesis process, large theoretical capacity and high working voltage, since 1985Delmas et al reported for the first time that it has been considered one of the most promising SIB positive electrode materials; however, P2 type Na x MnO 2 The anode material usually generates harmful P2-O2/OP4 phase change under high voltage, so that the structural stability is poor; meanwhile, due to the Jahn-Teller effect, the participation of mn3+ in the cycling process severely distorts the local lattice structure, resulting in insufficient battery performance.
In response to the above problems, doping strategies in which manganese is replaced with other metallic elements such as lithium, magnesium, aluminum, iron, copper, and nickel are considered as effective approaches to inhibit the P2-O2/OP4 phase transition and the ginger taylor effect, but they sacrifice the capacity contribution of manganese by reducing or completely inhibiting the redox activity of manganese. Therefore, developing new doping modification strategies to obtain higher specific capacity and higher stability cathode materials is critical to developing high performance energy storage and power sodium ion batteries.
Disclosure of Invention
The invention aims to provide a novel manganese-based layered oxide sodium ion battery anode material modified by doping heteropolyacid and a preparation method thereof, aiming at a plurality of problems of the existing P2-type manganese-based layered oxide; the invention firstly introduces the metal M, phosphorus and other elements in the heteropolyacid into the P2 type manganese-based layered oxide for doping modification to prepare the P2-Na 2/3 Mn 1-x (MP 1/12 ) x O 2 (abbreviated as P2-NMMPO), m= Mo, W, cr, V, x=0.001 to 0.3; the sodium ion battery anode material has the advantages of high initial discharge specific capacity, good cycle performance, long cycle life and the like; meanwhile, the positive electrode material of the sodium ion battery is prepared by a sol-gel method, has a P2 type layered structure, and is uniform in particle size, high in crystallinity and high in purity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the heteropolyacid modified layered oxide sodium battery anode material is characterized in that the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (MP 1/12 ) x O 2 Wherein m= Mo, W, cr, V, x=0.001 to 0.3.
Furthermore, the crystal phase structure of the positive electrode material of the sodium ion battery is a P2 type layered structure, the crystal system is a hexagonal crystal system, and the space group is P63/mmc.
The preparation method of the heteropolyacid modified layered oxide sodium battery anode material is characterized by comprising the following steps of:
step 1:1, dissolving a sodium source raw material and a complexing agent in deionized water according to a molar ratio of (1-2), and stirring for 1-3 hours at room temperature to obtain a solution A;
step 2: dissolving a manganese source raw material in deionized water, and stirring for 1-3 hours at normal temperature to obtain a solution B;
step 3: dissolving a combined raw material of a phosphorus source and an M source in ammonia water, and stirring for 1-3 h at room temperature to obtain a solution C; wherein m= Mo, W, cr, V;
step 4: dropwise adding the solution A into the solution B, heating in a water bath at 80-100 ℃ and stirring for 1-4h to obtain a solution D;
step 5: dropwise adding the solution C into the solution D, heating and stirring in a water bath at 80-100 ℃ for 6-10 h to obtain mixed gel;
step 6; drying the mixed gel in a blast drier at 120-200 ℃ for 12-24 hours to obtain xerogel;
step 7: grinding the xerogel into powder at room temperature, presintering for 4-8 h at 400-600 ℃, and sintering for 10-20 h at 750-1050 ℃ to obtain the target material.
Further, the combined raw materials of the sodium source raw material, the manganese source raw material and the phosphorus source and the M source satisfy the following proportion: (2/3): (1-x): (x/12): (x).
Further, in step 1, the sodium source raw material is at least one of sodium hydroxide, sodium nitrate, sodium carbonate, sodium acetate and sodium chloride, and the complexing agent is at least one of ascorbic acid, acetic acid, citric acid and malic acid.
In the step 2, the manganese source raw material is at least one of manganese acetate tetrahydrate, manganese carbonate, manganese sesquioxide, manganese tetraoxide, manganese chloride and manganese nitrate.
Further, in step 3, when m=mo, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium molybdate, phosphoric acid+molybdenum oxide, and ammonium phosphomolybdate; when m=w, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium tungstate, phosphoric acid+tungsten oxide, and ammonium phosphotungstate; when m=cr, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium chromate, phosphoric acid+chromium oxide and ammonium phosphate chromate; when m=v, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium vanadate, phosphoric acid+vanadium oxide and ammonium phosphovanadate.
In step 7, the pre-sintering and sintering are performed in the same atmosphere, specifically, an air atmosphere, an oxygen atmosphere, a nitrogen atmosphere or an argon atmosphere.
In step 7, the temperature rising rate of the presintering is 1-5 ℃/min, and the temperature rising rate of the sintering is 1-10 ℃/min.
Based on the technical scheme, the invention has the beneficial effects that:
1. the invention firstly introduces the metal element M, phosphorus and other elements in the heteropolyacid into the P2 type manganese-based layered oxide for doping modification to prepare the P2-Na 2/3 Mn 1-x (MP 1/12 ) x O 2 (abbreviated as P2-NMMPO), m= Mo, W, cr, V, x=0.001 to 0.3; the positive electrode material of the sodium ion battery has excellent electrochemical performance and high specific capacity and high stability. P2-Na 2/ 3 MnO 2 Is one of layered oxides, and involves Mn in the electrochemical oxidation-reduction process 3+ 、Mn 2+ And Mn of 4+ The theoretical capacity of the multi-electron oxidation-reduction reaction can reach 243mAh/g; however, P2-Na 2/3 MnO 2 The anode material usually generates harmful P2-O2/OP4 phase change under high voltage, so that the structural stability is poor; meanwhile, due to Jahn-Teller effect, mn 3+ The local lattice structure is severely distorted during cycling, resulting in insufficient cell performance; based on the method, the metal M, the metal P and other elements in the heteropoly acid are simultaneously introduced by adopting a one-step method.
Taking Mo as an example, introducing Mo and P elements into an initial phase for bulk phase doping, wherein Mo replaces part of Mn position, and the crystal is formedIn a +6 valence state, on the one hand, reduces Mn +3 Thereby reducing the ginger Taylor phase transition of the crystal structure; on the other hand, mo 6+ The oxygen layers have stronger covalent bond strength, so that the oxygen vacancy formation energy is enhanced, the release of oxygen under high voltage is prevented to a certain extent, and a more stable interlayer structure is formed. At the same time, consider Mn 3+ The reduction of (2) can reduce the initial discharge specific capacity, and further introduces a variable-valence P element; p element forms NaMnP in bulk localization 2 O 7 The olivine structure not only contributes to a part of the capacity, but also forms a dislocation of stacking faults in symbiosis with the layered structure, which further stabilizes the layered structure and suppresses the phase transition thereof. In addition, because the ionic radius of Mo and P elements is different from that of Mn and Na, the interlayer spacing is increased, and the intercalation and deintercalation of sodium ions are facilitated; doped P2-Na 2/ 3 Mn 1-x Mo x P x/12 O2 (x=0.001 to 0.3) and P2-Na 2/3 MnO 2 All belong to the P63/mmc space group, wherein 'P' represents the position of a triangular prism occupied by sodium ions, and '2' represents the number of manganese oxide layers in each repeatable unit; doping part of Na in crystal structure + Occupying the position of a triangular prism 2a, partially occupying the position of a triangular prism 2d, and Mn and Mo both occupying the position of an octahedron 2a to form a honeycomb ordered structure, wherein the stable interlayer structure is beneficial to Na + Is subject to electrochemical deintercalation. The invention is applied to P2-Na 2/3 MnO 2 Co-doping elements such as P and Mo to prepare the P2-Na 2/3 Mn 1-x Mo x P x/12 O 2 The lithium ion battery has higher specific discharge capacity, more stable cycle performance and a charge-discharge voltage platform which can be well matched with the positive electrode material, and is suitable for being used for making the requirements of medium-high energy density charge-discharge sodium ion batteries. When the charge-discharge multiplying power is 0.1C, the specific capacity of the P2 type layered oxide positive electrode material for the first time reaches more than 220mAh/g, and the P2-Na is unmodified 2/3 MnO 2 The discharge specific capacity of the first circle of the positive electrode material is only about 205 mAh/g. When the charge-discharge multiplying power is 0.5C, the specific capacity of the P2 type layered oxide anode material for the first time reaches 151mAh/g, the specific capacity of 101 circles in a circulation is 133.8mAh/g, and the capacity retention rate is as high as 88.6%; and unmodified P2-Na 2/3 MnO 2 The discharge specific capacity of the first circle of the positive electrode material is 153mAh/g, but the specific capacity of the 101 circles of the cycle is only 102.2mAh/g, and the capacity retention rate is only 66.8%.
2. The invention also provides a preparation method for doping modification of the novel manganese-based layered oxide sodium ion battery anode material; under the condition of heating in water bath, sodium source solution, manganese source solution, phosphorus source and molybdenum source (tungsten source, vanadium source or chromium source) solution are mixed in a certain sequence to form semitransparent mixed gel (namely precursor), and the precursor forms single-phase nano-grade P2-Na with good crystallization quality and uniform size in the high-temperature sintering process 2/3 Mn 1-x (MP 1/12 ) x O 2 The method comprises the steps of carrying out a first treatment on the surface of the The raw materials used in the preparation process are common chemical raw materials, the sources of raw materials and auxiliary materials are rich, and particularly, the sodium source raw materials are quite cheap, nontoxic and pollution-free, accord with the environment-friendly concept, and can also reduce the production cost for enterprises in the commercial production process; the equipment used in the preparation process is simple, the preparation process is easy to control, no special equipment is required, the preparation process is simple and easy to implement, and the requirement of large-scale industrial production can be met.
Drawings
FIG. 1 is a schematic diagram of the preparation flow of the novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material.
FIG. 2 is a schematic illustration of a novel manganese-based layered oxide sodium-ion battery anode material P2-Na doped and modified with heteropolyacid according to example 1 of the present invention 2/3 Mn 1-x Mo x P x/12 O 2 And primary phase P2-Na 2/3 MnO 2 XRD pattern comparison plot of (c).
FIG. 3 is a schematic illustration of a novel manganese-based layered oxide sodium-ion battery anode material P2-Na doped and modified with a heteropolyacid according to example 1 of the present invention 2/3 Mn 1-x Mo x P x/12 O 2 And primary phase P2-Na 2/3 MnO 2 A Scanning Electron Microscope (SEM) photograph of (b).
FIG. 4 is a schematic illustration of a novel manganese-based layered oxide sodium-ion battery anode material modified by doping with heteropolyacid in example 1 of the present inventionMaterial P2-Na 2/3 Mn 1-x Mo x P x/12 O 2 And primary phase P2-Na 2/3 MnO 2 First charge-discharge curve at 0.1C.
FIG. 5 is a schematic illustration of a novel manganese-based layered oxide sodium-ion battery anode material P2-Na doped and modified with a heteropolyacid according to example 1 of the present invention 2/3 Mn 1-x Mo x P x/12 O 2 And primary phase P2-Na 2/3 MnO 2 The structure of the button half cell assembled by the electrodes is schematically shown.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The embodiment provides a novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material, wherein the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (MoP 1/12 ) x O 2 X=0.01; the positive electrode material of the sodium ion battery is prepared by adopting a flow shown in figure 1, manganese acetate tetrahydrate and sodium carbonate are respectively used as a manganese source and a sodium source, citric acid is used as a complexing agent, ammonium phosphomolybdate is used as a phosphorus source and a molybdenum source, and ammonia water and deionized water are used as solvents; the method specifically comprises the following steps:
step 1: dissolving 0.04mol of citric acid and 0.021mol of sodium carbonate in 40mL of deionized water, and stirring for 1h at room temperature to obtain a mixed solution A;
step 2: dissolving 0.06mol of manganese acetate tetrahydrate in 40mL of deionized water, and stirring for 1h at normal temperature to obtain a solution B;
step 3: will be 4.98X10 -5 Dissolving mol of ammonium phosphomolybdate in 10mL of ammonia water, and stirring for 1h at room temperature to obtain a solution C;
step 4: slowly dripping the mixed solution A into the solution B, heating in a water bath at 85 ℃ and stirring for 60min to obtain a mixed solution D;
step 5: slowly dripping the solution C into the mixed solution D to obtain mixed sol; heating and stirring for 6 hours in a water bath at 85 ℃ to obtain mixed gel;
step 6: drying the mixed gel in a blast drier at 200 ℃ for 12 hours to obtain xerogel;
step 7: grinding xerogel into powder at room temperature by an agate mortar, transferring the powder into a ceramic boat, placing the ceramic boat in a muffle furnace, presintering the powder for 6 hours at 450 ℃ at a heating rate of 3 ℃/min, and sintering the powder for 15 hours at 950 ℃ at a heating rate of 2 ℃/min to prepare the heteropolyacid doped and modified novel manganese-based layered oxide sodium ion battery anode material P2-Na 2/ 3 Mn 0.99 (MoP 1/12 ) 0.01 O 2 。
Meanwhile, in order to illustrate the beneficial effects of the invention, a primary phase (blank phase) P2-Na is adopted 2/3 MnO 2 As a comparative example, the preparation procedure of the comparative example differs from that of the present example only in that: step 3: 10mL of ammonia water is directly used as solution C to prepare initial phase (blank phase) P2-Na 2/3 MnO 2 A positive electrode material of a sodium ion battery.
XRD measurements were performed on the positive electrode materials of sodium-ion batteries of the present example and comparative example, and the results are shown in FIG. 2, which shows that the present example and comparative example are both typical P2-type layered structures, and diffraction peaks correspond to P2-Na 2/3 MnO 2 The structure, heteropoly acid modification does not affect the parent compound P2-Na 2/3 MnO 2 Also for the presence of significant impurity phases. Positive electrode material P2-Na for sodium ion battery in this example and comparative example 2/3 MnO 2 As shown in FIG. 3, the results of SEM test are shown, and it can be seen that the positive electrode material P2-Na of sodium ion battery in this example 2/3 Mn 0.99 (MoP 1/12 ) 0.01 O 2 The particles are similar to spherical nano-scale to submicron-scale lamellar particles, are uniformly distributed and have an average particle diameter of about 3-5 um; the positive electrode material of the sodium ion battery in the comparative example is polygonal particles, and the average particle diameter is about 5-7 um.
Preparing an electrode by using a sodium ion battery anode material and an acetylene black conductive agent and polyvinylidene fluoride (Polyvinylidene Fluoride, PVDF) binder according to a mass ratio of 80:15:5; the specific process is as follows: first, the positive electrode is formedMixing the material and a conductive agent, weighing the materials (active substance of the positive electrode material 0.4g and acetylene black of the conductive agent 0.075 g) in a ratio of 80:15, and grinding in an agate mortar until the materials are fully and uniformly mixed, wherein the grinding time is more than or equal to 30min; then, adding 1ml of a pre-prepared PVDF solution with the concentration of 2.5wt%, and grinding for 20min again to obtain slurry with the three components uniformly mixed; then, uniformly coating the obtained slurry on the surface of the cleaned dry aluminum foil pole fluid by using a precise scraper, and baking the coated aluminum foil pole piece in a blast drying oven at 80 ℃ for 2 hours; finally, cutting the aluminum foil pole piece which is dried in the forced air drying oven, wherein the diameter of the pole piece is 12mm, drying the cut pole piece in the vacuum drying oven for 20 hours at 105 ℃, transferring the dried pole piece into a drying dish for standing for standby, and preventing moisture absorption; the active material loading of each pole piece is less than or equal to 4.0mg/cm 2 ) Is 2.28-2.34mg/cm 2 . Assembling the obtained electrode plate into a button type half cell for electrochemical performance test, and completing the half cell assembly in a stainless steel glove box filled with Ar; in this example, CR2025 button cell was used, sodium sheet was used as counter electrode, membrane was glass fiber GF/F, and electrolyte consisted of 1mol/L NaPF 6 Dissolving into a mixed solution of EC and DEC in a volume ratio of 1:1 to form; the construction of the CR2025 button cell is shown in FIG. 5. The constant current charge and discharge test was performed on button cells made of the positive electrode materials of sodium ion batteries in this example and comparative example, and the results are shown in FIG. 4, which shows that the sodium ion positive electrode materials P2-Na in this example 2/3 Mn 0.99 (MoP 1/12 ) 0.01 O 2 The initial discharge specific capacity of about 220mAh/g is obtained under the 0.1C multiplying power, and after 101 circles of circulation under the 0.5C multiplying power, the capacity retention rate is up to 88.6%; while in comparative example, the sodium ion positive electrode material P2-Na 2/3 MnO 2 The initial discharge specific capacity of only 205mAh/g is obtained at the 0.1C multiplying power, and the capacity retention rate is as high as 66.8% after 101 circles of circulation at the 0.5C multiplying power.
Example 2
The embodiment provides a novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material, wherein the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (WP 1/12 ) x O 2 X=0.05; the positive electrode material of the sodium ion battery is prepared by adopting the same procedure as in the embodiment 1, and the only difference is that: step 3: will be 2.49×10 -4 The mol ammonium phosphotungstate was dissolved in 50mL of aqueous ammonia and stirred at room temperature for 1h to give solution C.
Through electrochemical performance test, the novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material P2-Na in the embodiment 2/3 Mn 0.95 (WP 1/12 ) 0.05 O 2 An effect approximately equivalent to that of embodiment 1 can be achieved.
Example 3
The embodiment provides a novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material, wherein the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (VP 1/12 ) x O 2 X=0.02; the positive electrode material of the sodium ion battery is prepared by adopting the same procedure as in the embodiment 1, and the only difference is that: step 3: will be 9.96×10 -5 The mol ammonium phosphomolybdate was dissolved in 20mL of aqueous ammonia and stirred at room temperature for 1h to give solution C.
Through electrochemical performance test, the novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material P2-Na in the embodiment 2/3 Mn 0.98 (VP 1/12 ) 0.02 O 2 An effect approximately equivalent to that of embodiment 1 can be achieved.
Example 4
The embodiment provides a novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material, wherein the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (MoP 1/12 ) x O 2 X=0.15; the positive electrode material of the sodium ion battery is prepared by adopting the same procedure as in the embodiment 1, and the only difference is that: step 3: will be 7.47×10 -4 The mol ammonium phosphomolybdate was dissolved in 150mL of aqueous ammonia and stirred at room temperature for 1h to give solution C.
Through the test of the electrochemical performance of the material,novel heteropolyacid doped and modified manganese-based layered oxide positive electrode material P2-Na of sodium ion battery in embodiment 2/3 Mn 0.85 (MoP 1/12 ) 0.15 O 2 An effect approximately equivalent to that of embodiment 1 can be achieved.
Example 5
The embodiment provides a novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material, wherein the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (MoP 1/12 ) x O 2 X=0.05; the positive electrode material of the sodium ion battery is prepared by adopting the same procedure as in the embodiment 1, and the only difference is that: step 3: will be 2.49×10 -4 The mol ammonium phosphomolybdate was dissolved in 50mL of aqueous ammonia and stirred at room temperature for 1h to give solution C.
Through electrochemical performance test, the novel heteropolyacid doped and modified manganese-based layered oxide sodium ion battery anode material P2-Na in the embodiment 2/3 Mn 0.95 (MoP 1/12 ) 0.05 O 2 An effect approximately equivalent to that of embodiment 1 can be achieved.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.

Claims (9)

1. The heteropolyacid modified layered oxide sodium battery anode material is characterized in that the chemical expression of the sodium ion battery anode material is as follows: P2-Na 2/3 Mn 1-x (MP 1/12 ) x O 2 Wherein m= Mo, W, cr, V, x=0.001 to 0.3.
2. The heteropolyacid modified layered oxide sodium battery positive electrode material according to claim 1, wherein the crystalline phase structure of the sodium ion battery positive electrode material is a P2 layered structure, the crystal system is a hexagonal crystal system, and the space group is P63/mmc.
3. The method for preparing the heteropolyacid modified layered oxide sodium battery positive electrode material according to claim 1, comprising the steps of:
step 1:1, dissolving a sodium source raw material and a complexing agent in deionized water according to a molar ratio of (1-2), and stirring for 1-3 hours at room temperature to obtain a solution A;
step 2: dissolving a manganese source raw material in deionized water, and stirring for 1-3 hours at normal temperature to obtain a solution B;
step 3: dissolving a combined raw material of a phosphorus source and an M source in ammonia water, and stirring for 1-3 h at room temperature to obtain a solution C; wherein m= Mo, W, cr, V;
step 4: dropwise adding the solution A into the solution B, heating in a water bath at 80-100 ℃ and stirring for 1-4h to obtain a solution D;
step 5: dropwise adding the solution C into the solution D, heating and stirring in a water bath at 80-100 ℃ for 6-10 h to obtain mixed gel;
step 6; drying the mixed gel in a blast drier at 120-200 ℃ for 12-24 hours to obtain xerogel;
step 7: grinding the xerogel into powder at room temperature, presintering for 4-8 h at 400-600 ℃, and sintering for 10-20 h at 750-1050 ℃ to obtain the target material.
4. The method for preparing a heteropolyacid modified layered oxide sodium battery positive electrode material according to claim 3, wherein the sodium source raw material, the manganese source raw material and the combined raw materials of the phosphorus source and the M source satisfy the following proportions: (2/3): (1-x): (x/12): (x).
5. The method for preparing a layered oxide sodium battery positive electrode material modified by heteropolyacid according to claim 3, wherein in the step 1, the sodium source raw material is at least one of sodium hydroxide, sodium nitrate, sodium carbonate, sodium acetate and sodium chloride, and the complexing agent is at least one of ascorbic acid, acetic acid, citric acid and malic acid.
6. The method for preparing a layered oxide sodium battery positive electrode material modified by heteropolyacid according to claim 3, wherein in the step 2, the manganese source raw material is at least one of manganese acetate tetrahydrate, manganese carbonate, manganese sesquioxide, manganese tetraoxide, manganese chloride and manganese nitrate.
7. The method for preparing a layered oxide sodium battery positive electrode material modified by heteropolyacid according to claim 3, wherein in step 3, when m=mo, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium molybdate, phosphoric acid+molybdenum oxide, and ammonium phosphomolybdate; when m=w, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium tungstate, phosphoric acid+tungsten oxide, and ammonium phosphotungstate; when m=cr, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium chromate, phosphoric acid+chromium oxide and ammonium phosphate chromate; when m=v, the combined raw material of the phosphorus source and the M source is at least one of phosphoric acid+ammonium vanadate, phosphoric acid+vanadium oxide and ammonium phosphovanadate.
8. The method for preparing a layered oxide sodium battery positive electrode material modified by heteropolyacid according to claim 3, wherein in step 7, the pre-sintering and sintering are performed in the same atmosphere, specifically, an air atmosphere, an oxygen atmosphere, a nitrogen atmosphere or an argon atmosphere.
9. The method for preparing a layered oxide sodium battery positive electrode material modified by heteropolyacid according to claim 3, wherein in the step 7, the temperature rising rate of presintering is 1-5 ℃/min, and the temperature rising rate of sintering is 1-10 ℃/min.
CN202211584886.XA 2022-12-09 2022-12-09 Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof Pending CN116101994A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116779832A (en) * 2023-08-25 2023-09-19 江苏正力新能电池技术有限公司 Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116779832A (en) * 2023-08-25 2023-09-19 江苏正力新能电池技术有限公司 Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof
CN116779832B (en) * 2023-08-25 2023-10-27 江苏正力新能电池技术有限公司 Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof

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