CN115490267A - High-air-stability power type layered oxide positive electrode material and preparation method thereof - Google Patents
High-air-stability power type layered oxide positive electrode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002759 woven fabric Substances 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C01G53/00—Compounds of nickel
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a power type layered oxide positive electrode material with high air stability and a preparation method thereof. The anode material is P2 type layered metal oxide with a chemical general formula of Na x M a Cu b RE c O 2 Wherein x is more than or equal to 0.6 and less than or equal to 0.7<a≤0.7，0<b≤0.3，0<c is less than or equal to 0.05; wherein M is one or more of Fe, co, ni, mn and Ti, and RE is one of Y, la, ce, pr, nd, dy, sm, eu, gd, tb and Yb. The preparation method comprises the steps of obtaining a precursor by a ball milling method, and calcining step by a solid-phase sintering method to synthesize the target material. The cathode material provided by the invention has the advantages of excellent air stability, simple preparation method, low production and storage cost and high power, and can meet the requirement of the power density of the sodium-ion battery and the large-scale development and application of the low-cost high-power-density sodium-ion battery.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and relates to a power type layered oxide positive electrode material with high air stability and a preparation method thereof.
Background
The sodium ion battery is an important candidate for a large-scale energy storage system such as the future wind, the photoelectricity and the like due to the advantages of abundant earth reserves, low cost, unique battery safety characteristics and the like of sodium, so that high requirements are provided for the cycle life, the power characteristics and the manufacturing performance of materials of the battery. The commercial application of the layered sodium ion transition metal oxide is seriously hindered by the problems that the layered sodium ion transition metal oxide has insufficient power density, the phase change reversibility of the material structure is poor, the electrode/electrolyte interface is unstable, and the chemical deterioration is easy to occur when the layered sodium ion transition metal oxide is exposed in the air in the charge and discharge processes.
Disclosure of Invention
The invention provides a power type layered oxide anode material with high air stability, wherein the anode material is a P2 phase; the chemical formula is Na x M a Cu b RE c O 2 Wherein x is more than or equal to 0.6 and less than or equal to 0.7<a≤0.7，0<b≤0.3，0<c is less than or equal to 0.05; wherein M is one or more of Fe, co, ni, mn and Ti, and RE is one of Y, la, ce, pr, nd, dy, sm, eu, gd, tb and Yb.
The cathode material is in NaMO 2 On the basis of the anode material, proper copper ions are introduced firstly, so that the air stability of the anode material is effectively improved; secondly, by introducing rare earth element ions with a special 4f5d electronic structure, the power density is improved and the oxygen ion redox stability is stabilized; finally, the problems of poor air stability and low power density of the sodium-based layered transition metal oxide are solved by a combined structure modulation method.
The second aspect of the present invention also provides a preparation method of the power type layered oxide positive electrode material with high air stability, which comprises the following steps:
step 1: dispersing sodium salt, a transition metal compound, a copper compound and a rare earth oxide in N-methyl pyrrolidone according to a stoichiometric ratio of x: a: b: c, wherein x is more than or equal to 0.6 and less than or equal to 0.7,0.7 yarn-woven fabrics a are less than or equal to 0.8,0 yarn-woven fabrics b are less than or equal to 0.3,0 yarn-woven fabrics c are less than or equal to 0.05, and uniformly mixing; transferring the mixture to an agate ball milling tank, and sealing; placing the agate ball milling tank on a planetary ball mill, and carrying out wet ball milling for 12-24h at the ball milling speed of 400-800rpm; drying after the ball milling is finished to obtain a precursor;
and 2, step: weighing a proper amount of precursor powder in the step 1, and pressing the powder into a wafer with the diameter of 14mm and the thickness of 1-2mm under the pressure of 10-20 MPa; placing the sheet precursor into a tube furnace, calcining in the atmosphere of air or oxygen, heating to 700-1100 ℃ at the speed of 5-15 ℃/min, and calcining for 5-15h; cooling and grinding into powder to obtain an initial cathode material;
and step 3: pressing the initial anode material in the step 2 under the pressure of 10-20MPa to form a wafer with the diameter of 14mm and the thickness of 1-2mm, calcining in the atmosphere of air or oxygen, raising the temperature to 850-1050 ℃ at the speed of 5-15 ℃/min, and calcining for 12-48h; cooling to room temperature along with the furnace to obtain the power type layered oxide anode material with high air stability.
According to the preparation method provided by the invention, the sodium salt is at least one of sodium carbonate, sodium peroxide and sodium hydroxide.
According to the preparation method provided by the invention, the transition metal salt is at least one of acetate, carbonate or oxide of the transition metal.
According to the preparation method provided by the invention, the transition metal can be selected from one or a mixture of any of Fe, co, ni, mn and Ti.
According to the preparation method provided by the invention, the copper compound is one or a mixture of any more of acetate, carbonate or oxide of copper.
According to the preparation method provided by the invention, the rare earth oxide is Y 2 O 3 、La 2 O 3 、CeO 2 、Pr 2 O 3 、Nd 2 O 3 、Dy 2 O 3 、Sm 2 O 3 、Eu 2 O 3 、GdO 2 、Tb 2 O 3 And Yb 2 O 3 One kind of (1).
Preferably, the total mass of the agate balls adopted by the ball milling is 5-10 times of the total mass of the mixture.
Preferably, the volume of the precursor mixture is not more than 2/3 of the volume of the agate ball milling pot.
Technical effects
1. According to the invention, proper copper ions and rare earth ions with larger size are introduced in situ in the transition metal layer to form the P2-phase anode material, so that the synergistic effect of various metal ions in a layered structure is exerted, the air stability and the moisture resistance of the layered oxide anode material are effectively improved, the storage cost of the material is reduced, and the power density of the material is improved.
2. The invention adopts a solid-phase sintering method, and the precursors carry out solid-phase chemical reaction under certain reaction conditions, namely, the precursors are mutually diffused at high temperature in the calcining process, so that micro discrete particles gradually form a continuous solid-state layered structure, and the stable P2-type layered oxide material is obtained. The preparation method has simple process and low production cost.
3. In the invention, na prepared by a ball milling-solid phase synthesis method is used x M a Cu b RE c O 2 The cathode material has high reversible capacity and excellent rate performance. The first charge and discharge capacity is 122-175mAh/g respectively. Circulating at large multiplying power of 2C and 5C, the reversible capacity of 105-127mAh/g can be still maintained, and excellent multiplying power performance is shown.
4. In the invention, the crystal structure of the anode material is determined by X-ray diffraction technology (XRD), and XRD data results show that the material prepared by the synthesis method is P2 pure phase. In addition, the layered structure of the cathode material was hardly changed after being exposed to air for 30 days and soaked in deionized water at pH =7 and pH =12 for 3 days, indicating high air stability and moisture resistance of the cathode material.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is an XRD pattern of a cathode material obtained in example 1 under different environmental conditions;
FIG. 2 is an SEM photograph of the positive electrode material obtained in example 1;
FIG. 3 is a CV diagram of a positive electrode material obtained in example 2;
FIG. 4 is the first five-cycle charge-discharge curve of the Na-ion battery obtained in example 2, with a magnification of 0.1C;
fig. 5 is an XRD spectrum of the cathode material obtained in example 3;
FIG. 6 is the first five-cycle charge-discharge curve of the Na-ion battery obtained in example 3, with a magnification of 0.1C;
FIG. 7 shows the rate capability of the sodium ion battery obtained in example 3, with a test range of 0.1C-5C;
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a power type layered oxide positive electrode material with high air stability comprises the following steps: step 1: weighing corresponding mass of Na according to a molar ratio of 6.6 2 CO 3 、CuO、Fe 2 O 3 And Mn 2 O 3 Adding the precursor raw material into an agate ball milling tank, adding grinding balls with the total mass being 5 times of the total mass of the precursor mixture into the agate ball milling tank, carrying out wet ball milling for 24 hours at the speed of 400rpm, and drying after the ball milling is finished to obtain a precursor;
step 2: pressing the precursor in the step 1 under the pressure of 10MPa into a wafer with the diameter of 14mm and the thickness of 1mm, placing the obtained sheet sample into a tubular furnace, heating to 700 ℃ at the speed of 5 ℃/min under the atmosphere of oxygen, calcining for 6h, cooling to room temperature along with the furnace, grinding the wafer into powder, and obtaining an initial anode material;
and 3, step 3: pressing the initial positive electrode material in the step 2 under the pressure of 10MPa to form a wafer with the diameter of 14mm and the thickness of 1mm, heating to 950 ℃ at the speed of 8 ℃/min under the oxygen atmosphere, and calcining for 12h; cooling to room temperature along with the furnace to obtain the power type layered oxide anode material with high air stability, wherein the chemical formula of the anode material is Na 0.66 Cu 0.20 Fe 0.27 Mn 0.53 O 2 。
A series of characterization tests were performed on the positive electrode material obtained in this example: FIG. 1 is an XRD pattern of the obtained anode material, the material is P2 pure phase, belongs to a hexagonal system, has a space group of P63/mmc, and has obvious diffraction peak and higher intensity, which shows that the crystallinity of the sample is good. Furthermore, the layered structure was hardly changed after the material was exposed to air for 30 days and soaked in deionized water at pH =7 and pH =12 for 3 days, respectively, indicating high air stability and moisture resistance of the material. The SEM result in figure 2 shows that the particles are distributed more uniformly, the particle morphology is less regular, and the particle size is about 2-5 μm.
Example 2
A preparation method of a power type layered oxide positive electrode material with high air stability comprises the following steps:
step 1: according to a molar ratio of 6.6 2 CO 3 、CuO、Y 2 O 3 、Fe 2 O 3 And Mn 2 O 3 Adding the mixture serving as a precursor raw material into an agate ball-milling tank, adding grinding balls with the total mass being 8 times of the total mass of the precursor mixture into the tank, carrying out wet ball-milling for 18 hours at the speed of 600rpm, and drying after the ball-milling is finished to obtain a precursor;
and 2, step: pressing the precursor in the step 1 under the pressure of 15MPa into a wafer with the diameter of 14mm and the thickness of 1.5mm, placing the obtained sheet sample into a tubular furnace, heating to 700 ℃ at the speed of 5 ℃/min under the atmosphere of oxygen, calcining for 6h, cooling to room temperature along with the furnace, grinding the wafer into powder, and obtaining an initial anode material;
and step 3: pressing the initial anode material in the step 2 under the pressure of 15MPa into a wafer with the diameter of 14mm and the thickness of 1.5mm, heating to 950 ℃ at the speed of 8 ℃/min under the oxygen atmosphere, and calcining for 12h; cooling to room temperature along with the furnace to obtain the power type layered oxide anode material with high air stability, wherein the chemical formula of the anode material is Na 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 。
Performance testing
Carrying Na 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 The working electrode of the active material was prepared as follows:
step 1: the active substance Na in example 2 was added 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 The conductive agent acetylene black and the binder PVDF are ground and mixed uniformly in an agate mortar according to the mass ratio of 7Dispersing the uniformly mixed powder in a proper amount of N-methyl pyrrolidone solvent under stirring, and performing magnetic stirring and uniform mixing to obtain slurry;
and 2, step: uniformly coating the slurry obtained in the step 1 on a dry and clean aluminum foil by using a film coater, and then transferring the aluminum foil to a vacuum drying oven at 75 ℃ for drying for 24 hours to obtain a pole piece;
and step 3: compacting the pole piece obtained in the step 2 on a roller press, and then punching the pole piece into a wafer with the diameter of 12mm by using a button cell punching machine to obtain the Na-loaded wafer 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 A working electrode of active material.
In an argon glove box, will be loaded with Na 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 The working electrode of the active material is a positive electrode, electrolyte, a glass fiber diaphragm soaked by the electrolyte and a metal sodium sheet are used as negative electrodes to assemble a 2032 button cell. Wherein the electrolyte is a homogeneous mixed solution consisting of conductive salt, ethylene carbonate and propylene carbonate, and NaClO is contained in the solution 4 The concentration of (2) is 1mol/L, and the volume ratio of ethylene carbonate to propylene carbonate is 1. The electrochemical performance of the assembled cells was tested using a novyi charge-discharge tester.
FIG. 3 shows that the result shows that Na 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 The CV curve of (a) shows a sharp anodic peak at about 4.2V, indicating that there is an anion in the system participating in the electrochemical reaction and contributing to the capacity. Furthermore, as the number of cycles increases, the electrochemical polarization of the system gradually increases.
FIG. 4 shows Na 0.66 Cu 0.20 Y 0.005 Fe 0.265 Mn 0.53 O 2 The charge-discharge curve chart of the anode material. As can be seen from the figure, under the multiplying power of 0.1C and the voltage range of 1.5-4.5V (vs. Na +/Na), the first charge-discharge capacity of the material provided by the embodiment is up to 118-146mAh/g, the reversible capacity after 5 cycles of circulation is 140mAh/g, the capacity attenuation is small, and the electrochemical reversibility is high.
Example 3
A preparation method of a power type layered oxide positive electrode material with high air stability comprises the following steps:
step 1: according to a molar ratio of 6.6 3 COONa、(CH 3 COO) 2 Cu·H 2 O、(CH 3 COO) 3 Y·4H 2 O、(CH 3 COO) 2 Fe·H 2 O and (CH) 3 COO) 2 Mn·4H 2 Adding O serving as a precursor raw material into an agate ball milling tank, adding grinding balls with the total mass being 10 times of the total mass of the precursor mixture into the agate ball milling tank, carrying out ball milling for 12 hours at the speed of 800rpm, and drying after the ball milling is finished to obtain a precursor;
and 2, step: pressing the precursor in the step 1 into a wafer with the diameter of 14mm under the pressure of 20MPa, placing the obtained sheet sample into a tubular furnace, heating to 700 ℃ at the speed of 5 ℃/min under the atmosphere of oxygen, calcining for 6h, cooling to room temperature along with the furnace, and grinding the wafer into powder to obtain an initial anode material;
and step 3: pressing the initial positive electrode material in the step 2 under the pressure of 20MPa into a wafer with the diameter of 14mm and the thickness of 2mm, heating to 950 ℃ at the speed of 8 ℃/min in an oxygen atmosphere, and calcining for 12h; cooling to room temperature along with the furnace to obtain the power type layered oxide anode material with high air stability, wherein the chemical formula of the anode material is Na 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 。
XRD results showed (see FIG. 5), that Na was produced 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 The P2 type layered oxide belongs to a hexagonal system, the space group is P63/mmc, the diffraction peak is obvious, the intensity is high, and the crystallinity of the sample is good. Furthermore, the layered structure was hardly changed after the material was exposed to air for 30 days and soaked in deionized water at pH =7 and pH =12 for 3 days, respectively, indicating high air stability and moisture resistance of the material.
Performance testing
Loaded with Na x M a Cu b RE c O 2 The working electrode of the active material was prepared as follows:
step 1: the active substance Na in example 3 was added 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 Grinding and uniformly mixing the conductive agent acetylene black and the binder PVDF in an agate mortar according to the mass ratio of 7;
and 2, step: uniformly coating the slurry obtained in the step 1 on a dry and clean aluminum foil by using a film coater, and then transferring the aluminum foil to a vacuum drying oven at 75 ℃ for drying for 24 hours to obtain a pole piece;
and step 3: compacting the pole piece obtained in the step 2 on a roller press, and then punching the pole piece into a wafer with the diameter of 12mm by using a button cell punching machine to obtain the Na-loaded wafer 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 A working electrode of active material.
In an argon glove box, will be loaded with Na 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 The working electrode of the active material is a positive electrode, the glass fiber diaphragm soaked in the electrolyte and the metal sodium sheet are used as negative electrodes to assemble a 2032 button cell. Wherein the electrolyte is a homogeneous mixed solution consisting of conductive salt, ethylene carbonate and propylene carbonate, and NaClO is contained in the solution 4 The concentration of the ethylene carbonate is 1mol/L, and the volume ratio of the ethylene carbonate to the propylene carbonate is 1. (ii) a The electrochemical performance of the assembled cells was tested using a novyi charge-discharge tester.
FIG. 6 shows the results for Na 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 In the voltage range of 1.5-4.5V (vs. Na +/Na), the first charge-discharge capacity is up to 122-175mAh/g, the reversible capacity after 5 cycles of circulation is still up to 170mAh/g, and almost no capacity attenuation exists, which indicates that the electrochemical reversibility is high.
FIG. 7 shows Na 0.66 Cu 0.20 Y 0.01 Fe 0.26 Mn 0.53 O 2 And (3) a rate performance graph of the cathode material. As can be seen from the figure, the material provided by the embodiment can still provide the capacity of about 105-127mAh/g under the large multiplying power of 2C and 5C; then the multiplying power is recovered to 0.1C, and the reversible capacity is still 159.47mAh/g. Compared with the initial discharge capacity at 0.1C rate, the reversible capacity retention rate of the material is up to 93.02 percent, which shows that the material has good structural stability and excellent rate performance.
The above performance data indicate that Na is prepared by a solid phase reaction process x M a Cu b RE c O 2 Is P2 pure phase, is a power type layered oxide anode material with high air stability, and can be applied to sodium ion batteries.
Claims (9)
1. The power type layered oxide anode material with high air stability is characterized in that the anode material is a P2 phase; has a chemical general formula of Na x M a Cu b RE c O 2 Wherein x is more than or equal to 0.6 and less than or equal to 0.7<a≤0.8，0<b≤0.3，0<c is less than or equal to 0.05; wherein M is one or more of Fe, co, ni, mn and Ti, and RE is one of Y, la, ce, pr, nd, dy, sm, eu, gd, tb and Yb.
2. The high-air-stability power type layered oxide positive electrode material as claimed in claim 1, wherein the preparation method of the positive electrode material comprises the following steps:
step 1: dispersing sodium salt, a transition metal compound, a copper compound and a rare earth oxide in N-methyl pyrrolidone according to a stoichiometric ratio of x: a: b: c, wherein x is more than or equal to 0.6 and less than or equal to 0.7,0.7 yarn-woven fabrics a are less than or equal to 0.8,0 yarn-woven fabrics b are less than or equal to 0.3,0 yarn-woven fabrics c are less than or equal to 0.05, and uniformly mixing; transferring the mixture to an agate ball milling tank, and sealing; placing the agate ball-milling tank on a planetary ball mill, and carrying out wet ball milling for 12-24h at the ball-milling speed of 400-800rpm; drying after the ball milling is finished to obtain a precursor;
step 2: weighing a proper amount of precursor powder in the step 1, and pressing the powder into a wafer with the diameter of 14mm and the thickness of 1-2mm under the pressure of 10-20 MPa; placing the sheet precursor into a tube furnace, calcining in the atmosphere of air or oxygen, heating to 700-1100 ℃ at the speed of 5-15 ℃/min, and calcining for 5-15h; cooling and grinding into powder to obtain an initial cathode material;
and step 3: pressing the initial anode material in the step 2 under the pressure of 10-20MPa to form a wafer with the diameter of 14mm and the thickness of 1-2mm, calcining in the atmosphere of air or oxygen, raising the temperature to 850-1050 ℃ at the speed of 5-15 ℃/min, and calcining for 12-48h; cooling to room temperature along with the furnace to obtain the power type layered oxide anode material with high air stability.
3. The method for preparing a high-air-stability power-type layered oxide cathode material as claimed in claim 2, wherein the sodium salt in step 1 is at least one of sodium carbonate, sodium peroxide and sodium hydroxide.
4. The method for preparing a high-air-stability power-type layered oxide positive electrode material as claimed in claim 2, wherein the transition metal salt in step 1 is at least one selected from acetate, carbonate or oxide of a transition metal.
5. The preparation method of the high-air-stability power type layered oxide cathode material as claimed in claims 2 and 4, wherein the transition metal in the transition metal salt is one or a mixture of any of Fe, co, ni, mn and Ti.
6. The preparation method of the high-air-stability power type layered oxide positive electrode material as claimed in claim 2, wherein the copper compound is one or a mixture of any more of acetate, carbonate or oxide of copper.
7. The method for preparing high-air-stability power type layered oxide cathode material as claimed in claim 2, wherein the rare earth is oxidized in step 1The object is Y 2 O 3 、La 2 O 3 、CeO 2 、Pr 2 O 3 、Nd 2 O 3 、Dy 2 O 3 、Sm 2 O 3 、Eu 2 O 3 、GdO 2 、Tb 2 O 3 And Yb 2 O 3 To (3) is provided.
8. The preparation method of the high-air-stability power type layered oxide positive electrode material as claimed in claim 2, wherein the total mass of the agate balls adopted in the ball milling in the step 1 is 5-10 times of the total mass of the mixture.
9. The preparation method of the high-air-stability power type layered oxide cathode material as claimed in claim 2, wherein the volume of the precursor mixture is not more than 2/3 of the volume of the agate ball mill pot.
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