CN110197902B - Porous structure open walnut shell-shaped sodium ion battery positive electrode material and preparation method thereof - Google Patents
Porous structure open walnut shell-shaped sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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 discloses a porous structure open walnut shell-shaped sodium ion battery anode material and a preparation method thereof, wherein the structural formula of the anode material is Na0.67Ni1/3Co(1/3‑x)Mn1/3AlxO2，0≤x<1/3, respectively; the positive electrode material of the sodium ion battery has a porous structure and is in a walnut shell shape with an opening in the middle. The electrode material prepared by the invention has a structure which is beneficial to electron transmission and sodium ion diffusion, can buffer the volume strain in the charging and discharging process, has a large specific surface area, improves the contact area of an active substance and electrolyte, and enables the material to have excellent electrochemical performance.
Description
Technical Field
The invention relates to a preparation method of a chemical power supply electrode material, in particular to a porous walnut shell-shaped Na with an opening in the middle0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(0≤x<1/3) preparation method of positive electrode material of sodium ion battery.
Background
In recent years, with the gradual shortage of fossil energy, the development of new energy has become a research hotspot at present. The lithium ion battery as a mature energy storage system at present has many advantages, such as higher energy density, longer cycle life, environmental friendliness and the like. However, the lithium source has limited reserves and great development difficulty. And due to the continuous development of the lithium ion battery, the price of raw materials related to the lithium ion battery is also continuously increased, which limits the further development of the lithium ion battery. Compared with lithium element, sodium element belongs to the first main group and is relatively close to the first main group in physical and chemical properties, but the sodium element has wide sources and abundant reserves, and the development of the sodium ion battery by replacing lithium with sodium has great advantages in cost. Therefore, the sodium ion battery has wide development prospect as a new generation of energy storage device.
Although sodium ion batteries have many advantages, sodium atoms have a larger mass (about 3.3 times that of lithium atoms), resulting in a lower energy density; secondly, due to the larger radius of the sodium ions, the de-intercalation/intercalation diffusion of the sodium ions during the charge and discharge electrochemical reaction of the battery faces greater resistance. The electrochemical performance of lithium ion batteries still needs to be further improved. Sodium ion batteries face problems of low ionic conductivity, slow diffusion rate of sodium ions, and the like. Researches show that the electrochemical performance of the sodium-ion battery is closely related to the composition, morphology, microstructure and the like of electrode materials. There is a need in these areas to improve the electrochemical performance of sodium ion battery electrode materials by efficient design.
In the research on the relation between the cycle performance of a sodium-ion battery and the appearance and microstructure of an electrode material, Srinivasa nScadhavi et al prepare NaxMnO2+zHollow spheres and NaxMnO2+zMicron sheet, and comparing the electrochemical performance of the two, Na is foundxMnO2+zThe hollow sphere has higher circulation stability, and has 94mAh g after 100 cycles-1Specific discharge capacity, and NaxMnO2+zThe specific discharge capacity of the micron sheet is 73mAh g-1。(Bucher N,Hartung S,Nagasubramanian A,etal.Layered NaxMnO2+zin Sodium Ion Batteries-Influence of Morphology on CyclePerformance[J].ACS Applied Materials&Interfaces,2014,6(11):8059.)。
The porous structure material is beneficial to electron transmission and sodium ion diffusion in the electrochemical reaction process, can buffer the volume strain in the charge-discharge process, can effectively inhibit the structural collapse in the electrochemical reaction process, and improves the stability of the material, thereby improving the cycle performance of the material; in addition, the porous structure material has larger specific surface area, can provide more electrochemical reaction active sites in the electrochemical reaction process, and enables the material to have higher electrochemical activity, so that the porous structure electrode material has better potential application prospect.
Disclosure of Invention
The invention provides a porous structure open walnut shell-shaped sodium ion battery anode material and a preparation method thereof, and the method is based on that small molecular organic matters are adsorbed on a specific crystal face in the growth process of a precursor to change the growth of precursor crystal grains and prepare the precursor with a special shape, so that the porous structure open walnut shell-shaped sodium ion battery anode material with a larger specific surface area is finally prepared, the electrochemical performance of the material is improved, and the service performance of a sodium ion battery is improved.
The invention solves the technical problem and adopts the following technical scheme:
the invention firstly discloses a walnut shell-shaped sodium ion battery anode material with an opening in a porous structure, which is characterized in that: the structural formula of the positive electrode material of the sodium-ion battery is Na0.67Ni1/3Co(1/3-x)Mn1/3AlxO2，0≤x<1/3, respectively; the positive electrode material of the sodium ion battery has a porous structure and is in a walnut shell shape with an opening in the middle. The diameter of the long axis of the obtained open walnut shell-shaped sodium ion battery electrode material is about 2-5 mu m, and the diameter of the short axis is about 1-2 mu m.
The preparation method of the porous structure open walnut shell-shaped sodium ion battery anode material comprises the following steps: firstly, reacting a mixed aqueous solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt with an aqueous solution of soluble oxalate serving as a precipitator in a system of a micromolecular solvent to obtain a walnut-shaped precursor; and then mixing and calcining the walnut-shaped precursor, aluminum salt and sodium salt to obtain the open walnut shell-shaped sodium ion battery cathode material with the porous structure.
During precursor preparation: in the initial stage of the reaction, the concentration of reactants is high, a large number of crystal nuclei are generated, and small molecular organic matters in the solvent are selectively adsorbed on specific crystal faces of the crystal nuclei; in the later growth, the crystal face adsorbing the organic matter is inhibited from growing slowly, and the growth speed of other crystal faces is unchanged, so that a walnut-shaped precursor is finally formed.
During the mixed calcination process of the precursor, sodium salt and aluminum salt, the walnut-shaped appearance is converted into a porous and open walnut shell-shaped structure.
Specifically, the preparation method comprises the following steps:
(1) weighing soluble nickel salt, soluble cobalt salt and soluble manganese salt according to a stoichiometric ratio, and preparing a nickel-cobalt-manganese mixed aqueous solution with the total concentration of 0.2-1M; uniformly mixing the nickel-cobalt-manganese mixed aqueous solution with a small molecular organic solvent according to the volume ratio of 1-5:1 to obtain a solution A;
(2) uniformly mixing a soluble oxalate aqueous solution with the concentration of 0.2-10M and a small molecular organic solvent according to the volume ratio of 1-5:1 to obtain a solution B;
(3) adding the solution B into the solution A while stirring, and continuously stirring and reacting for 6-8h after adding to obtain a suspension C; the molar ratio of the sum of the molar amounts of the nickel ions, the cobalt ions and the manganese ions to the oxalate ions in the suspension C is 1: 1.1-10;
(4) centrifuging the suspension C to obtain precipitate, sequentially washing the precipitate with deionized water and ethanol, and drying at 30-100 deg.C for 6-24 hr to obtain walnut-shaped oxalate precursor MC2O4·wH2O, M ═ Mn, Ni, and Co;
(5) the precursor is fully mixed with sodium salt and aluminum salt according to the molar ratio of 1:0.70-0.80: x, then calcined for 4-8h at the temperature of 450-500 ℃ in the air atmosphere, and then calcined for 15-24h at the temperature of 700-900 ℃ to obtain the target product of the porous structure open walnut shell-shaped sodium ion battery anode material Na0.67Ni1/3Co(1/3-x)Mn1/3AlxO2，0≤x<1/3。
Further: the soluble nickel salt is at least one of nickel acetate, nickel sulfate, nickel chloride or nickel nitrate; the soluble cobalt salt is at least one of cobalt acetate, cobalt sulfate, cobalt chloride or cobalt nitrate; the soluble manganese salt is at least one of manganese acetate, manganese sulfate, manganese chloride or manganese nitrate; the sodium salt is at least one of sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate or sodium hydroxide; the aluminum salt is at least one of aluminum nitrate, aluminum sulfate and aluminum isopropoxide; the soluble oxalate is at least one of oxalic acid, ammonium oxalate, ammonium hydrogen oxalate or sodium oxalate; the micromolecular solvent is Tween 80 (C)64H124O26) Isooctane (C)18H18) Or dichloromethane (CH)2Cl2) One kind of (1).
Compared with the prior art, the invention has the beneficial effects that:
the invention regulates and controls the growth process of the precursor based on a small molecular organic matter crystal face regulation and control method, the crystal face adsorbed by the small molecular organic matter is inhibited from growing slowly due to growth, the growth speed of other crystal faces is unchanged, finally, the walnut-shaped precursor is formed, and the porous structure open walnut shell-shaped sodium ion battery anode material can be obtained through sodium mixing and aluminum mixing calcination. The preparation method has simple process, is easy to implement and is beneficial to popularization and application. The prepared open walnut shell-shaped sodium ion battery electrode material has a structure which is beneficial to electron transmission and lithium ion diffusion, and can buffer structural strain in the charge-discharge process, so that the electrochemical performance of the material is improved; the structure of the material is beneficial to improving the specific surface area of the material, can increase the contact area of the active substance and the electrolyte, provides more active sites in the electrochemical reaction process, and is beneficial to improving the electrochemical performance of the material.
Drawings
FIG. 1 is a FESEM image (a and b at different magnifications) and a TEM image (c) of a ternary oxalate precursor prepared according to example 1 of the invention;
FIG. 2 shows shell-like ternary Na of open walnut prepared in example 1 of the present invention0.67Ni1/3Co(1/3-x)Mn1/3AlxO2An X-ray diffraction (XRD) pattern of (X ═ 0.03);
FIG. 3 shows shell-like ternary Na of open walnut prepared in example 1 of the present invention0.67Ni1/3Co(1/3-x)Mn1/3AlxO2FESEM images of (x ═ 0.03) (a and b at different magnifications);
FIG. 4 shows shell-like ternary Na of open walnut prepared in example 1 of the present invention0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(x ═ 0.03) graph of rate performance at different rates;
FIG. 5 shows shell-like ternary Na of open walnut prepared in example 1 of the present invention0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(x ═ 0.03) charge and discharge curves at different current densities;
FIG. 6 shows shell-like ternary Na of open walnut prepared in example 1 of the present invention0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(x ═ 0.03) cycle performance plot at 0.1C magnification;
FIG. 7 is an FESEM image (a and b are at different magnifications) and a TEM image (c) of walnut-like ternary oxalate precursor powder prepared in example 2 of the present invention;
FIG. 8 shows shell-like ternary Na of open walnut prepared in example 2 of the present invention0.67Ni1/3Co1/3Mn1/3xO2X-ray diffraction (XRD) pattern of (a);
FIG. 9 shows shell-like ternary Na of open walnut prepared in example 2 of the present invention0.67Ni1/3Co1/3Mn1/3xO2FESEM (a and b at different magnifications) and TEM (c);
FIG. 10 shows shell-like ternary Na of open walnut prepared in example 2 of the present invention0.67Ni1/3Co1/3Mn1/3xO2A cycle performance diagram under different multiplying power;
FIG. 11 shows shell-like ternary Na of open walnut prepared in example 2 of the present invention0.67Ni1/3Co1/3Mn1/3xO2A charge-discharge curve chart under different current densities;
FIG. 12 shows shell-like ternary Na of open walnut prepared in example 2 of the present invention0.67Ni1/3Co1/3Mn1/3xO2Cycle performance plot at 0.1C.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: walnut shell-like ternary Na with opening in porous structure0.67Ni1/3Co(1/3-x)Mn1/3AlxO2Preparation of (x ═ 0.03)
The target product of this example is Na0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(x is 0.03), the used precipitant is oxalic acid solution, and the preparation method is as follows:
at room temperature, adding 50mL of mixed aqueous solution of nickel acetate, cobalt acetate and manganese acetate with the total concentration of 0.5M into 40mL of Tween 80, and uniformly mixing to obtain a solution A; adding 50mL of oxalic acid aqueous solution with the concentration of 1M into 40mL of Tween 80, and uniformly mixing to obtain solution B; and dropwise adding the solution B into the solution A while stirring, and continuously stirring and reacting for 8 hours after the dropwise adding is finished to obtain a suspension C. And (3) carrying out centrifugal separation on the suspension C to obtain a precipitate, washing the precipitate by using deionized water and ethanol in sequence, and then drying at 80 ℃ for 12h to obtain a walnut-shaped oxalate precursor.
Fully mixing an oxalate precursor, sodium bicarbonate and aluminum nitrate according to a molar ratio of 1:0.75:0.03, calcining at 480 ℃ for 5 hours in an air atmosphere, and calcining at 800 ℃ for 15 hours to obtain a target product of walnut shell-shaped ternary Na with a porous structure0.67Ni1/3Co(1/3-x)Mn1/3AlxO2(x ═ 0.03) material.
FIG. 1 is a FESEM image (FIGS. 1(a) and (b)) and a TEM image (FIG. 1(c)) of a walnut-like oxalate precursor at different magnifications, from which it can be seen that the walnut-like precursor has a major axis diameter of about 3-4 μm and a minor axis diameter of about 1-2 μm.
FIG. 2 is the XRD pattern of the target product obtained in this example, from which it can be seen that the product is Na form P20.67Ni1/ 3Co(1/3-x)Mn1/3AlxO2(x＝0.03)。
FIG. 3 is an FESEM image of the target product obtained in this example under different magnifications, and it can be seen from the FESEM image that the product is a porous structure and is in the shape of a walnut shell with an open center, the major axis diameter is about 3-4 μm, and the minor axis diameter is about 1-2 μm.
The shell-shaped ternary Na of the opened walnut of the embodiment0.67Ni1/3Co(1/3-x)Mn1/3AlxO2The (x is 0.03), acetylene black and polyvinylidene fluoride (PVDF) are fully mixed according to the mass ratio of 7:2:1, N-methyl pyrrolidone (NMP) is added to be mixed into paste, the paste is uniformly coated on an aluminum foil, the coating thickness is 75 mu m, and the positive plate is prepared after drying and compacting at 70 ℃. A metal sodium sheet is taken as a negative electrode, whatman G/F type glass fiber is taken as a diaphragm, and 1M NaPF6The solution (dimethyl ether) is used as electrolyte and is filled in an argon glove box to prepare a CR2032 type battery.
As shown in FIG. 4, the specific discharge capacities of the electrodes at current densities of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C were 123.4, 115.8, 109.1, 96.6, 88.8, 80.9 and 74.7mAh g-1(ii) a After 5 times of circulation under the multiple multiplying power, the current density returns to 0.1C again, and the specific discharge capacity is 119.5mAh g-1. Fig. 5 is a charge-discharge curve of the material under different current densities.
As shown in FIG. 6, it can be seen from the cycle performance chart at 0.1C that the capacity retention rate can reach 75.4% after 100 cycles, which indicates that the material has excellent cycle performance.
Example 2: walnut shell-like ternary Na with opening in porous structure0.67Ni1/3Co1/3Mn1/3O2Preparation of (x ═ 0)
The target product of this example is Na0.67Ni1/3Co1/3Mn1/3O2The precipitant is oxalic acid solution, and the preparation method is as follows:
at room temperature, adding 50mL of mixed aqueous solution of nickel acetate, cobalt acetate and manganese acetate with the total concentration of 0.5M into 40mL of Tween 80, and uniformly mixing to obtain a solution A; adding 50mL of oxalic acid aqueous solution with the concentration of 1M into 40mL of Tween 80, and uniformly mixing to obtain solution B; and adding the solution B into the solution A while stirring, and continuously stirring and reacting for 8 hours after adding to obtain a suspension C. And (3) carrying out centrifugal separation on the suspension C to obtain a precipitate, washing the precipitate by using deionized water and ethanol in sequence, and then drying at 80 ℃ for 12h to obtain a walnut-shaped oxalate precursor.
Mixing oxalate precursor and sodium bicarbonate at a molar ratio of 1:0.75, calcining at 480 deg.C for 5 hr in air atmosphere, and heating at 800 deg.CCalcining for 15h to obtain the target product of the walnut shell-shaped ternary Na with the porous structure and the opening0.67Ni1/3Co1/ 3Mn1/3O2。
FIG. 7 is a FESEM image (FIGS. 7(a) and (b)) and a TEM image (FIG. 7(c)) of an oxalate precursor at different magnifications, from which it can be seen that the walnut-like oxalate precursor has a major axis diameter of about 3-4 μm and a minor axis diameter of about 1-2 μm.
FIG. 8 is the XRD pattern of the target product obtained in this example, from which it can be seen that the product is Na form P20.67Ni1/ 3Co1/3Mn1/3O2。
FIG. 9 is a FESEM image (FIGS. 9(a) and (b)) and a TEM image (FIG. 9(c)) of the target product obtained in this example at different magnifications, and it can be seen that the product has a porous structure in the shape of a walnut shell with an open center, a major axis diameter of about 3 to 4 μm and a minor axis diameter of about 1 to 2 μm.
Mixing Na0.67Ni1/3Co1/3Mn1/3O2The material was formed into electrode sheets according to the method of example 1, and assembled into a CR2032 type battery in an argon glove box. The results of constant current charge and discharge tests at 25 ℃ were shown in fig. 10. The specific discharge capacity of the electrode is 119.3, 106.6, 95.8, 89.5, 82.4, 75.5 and 63.6 mAh.g at the current density of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C-1(ii) a After 5 times of circulation under the multiple multiplying power, the discharge current returns to 0.1C again, and the specific discharge capacity is 110.5mAh g-1. Fig. 11 is a charge-discharge curve of the material under different current densities.
As shown in fig. 12, it can be seen from the cycle performance chart at the current density of 0.1C that the capacity retention rate was 50.4% at 100 cycles.
The foregoing is considered as illustrative and not restrictive, and any modifications, equivalents and improvements made within the spirit and scope of the present invention are intended to be included therein.
Claims (4)
1. Porous structure is openedThe preparation method of the pecan shell-shaped sodium ion battery anode material is characterized by comprising the following steps of: the structural formula of the positive electrode material of the sodium-ion battery is Na0.67Ni1/3Co(1/3-x)Mn1/3AlxO2，0≤x<1/3, respectively; the positive electrode material of the sodium ion battery has a porous structure and is in a walnut shell shape with an opening in the middle;
firstly, reacting a mixed aqueous solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt with an aqueous solution of soluble oxalate serving as a precipitator in a system of a small molecular solvent to obtain a walnut-shaped precursor; then mixing and calcining the walnut-shaped precursor, aluminum salt and sodium salt to obtain a walnut shell-shaped sodium ion battery anode material with an open porous structure; the method comprises the following steps:
(1) weighing soluble nickel salt, soluble cobalt salt and soluble manganese salt according to a stoichiometric ratio, and preparing a nickel-cobalt-manganese mixed aqueous solution with the total concentration of 0.2-1M; uniformly mixing the nickel-cobalt-manganese mixed aqueous solution with a small molecular organic solvent according to the volume ratio of 1-5:1 to obtain a solution A;
(2) uniformly mixing a soluble oxalate aqueous solution with the concentration of 0.2-10M and a small molecular organic solvent according to the volume ratio of 1-5:1 to obtain a solution B;
(3) adding the solution B into the solution A while stirring, and continuously stirring and reacting for 6-8h after adding to obtain a suspension C; the molar ratio of the sum of the molar amounts of the nickel ions, the cobalt ions and the manganese ions to the oxalate ions in the suspension C is 1: 1.1-10;
(4) centrifuging the suspension C to obtain precipitate, sequentially washing the precipitate with deionized water and ethanol, and drying at 30-100 deg.C for 6-24 hr to obtain walnut-shaped oxalate precursor MC2O4·wH2O, M ═ Mn, Ni, and Co;
(5) the precursor is fully mixed with sodium salt and aluminum salt according to the molar ratio of 1:0.70-0.80: x, then calcined for 4-8h at the temperature of 450-500 ℃ in the air atmosphere, and then calcined for 15-24h at the temperature of 700-900 ℃ to obtain the target product of the porous structure open walnut shell-shaped sodium ion battery anode material Na0.67Ni1/3Co(1/3-x)Mn1/3AlxO2，0≤x<1/3。
2. The method of claim 1, wherein:
the soluble nickel salt is at least one of nickel acetate, nickel sulfate, nickel chloride or nickel nitrate;
the soluble cobalt salt is at least one of cobalt acetate, cobalt sulfate, cobalt chloride or cobalt nitrate;
the soluble manganese salt is at least one of manganese acetate, manganese sulfate, manganese chloride or manganese nitrate;
the sodium salt is at least one of sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate or sodium hydroxide;
the aluminum salt is at least one of aluminum nitrate, aluminum sulfate or aluminum isopropoxide.
3. The method of claim 1, wherein: the soluble oxalate is at least one of oxalic acid, ammonium oxalate, ammonium hydrogen oxalate or sodium oxalate.
4. The method of claim 1, wherein: the micromolecular solvent is one of tween 80, isooctane or dichloromethane.
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| JP2015176678A (en) * | 2014-03-13 | 2015-10-05 | 日産自動車株式会社 | Positive electrode active material for sodium ion battery and sodium ion battery using the same |
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