CN116014119A - Mixed type sodium ion battery positive electrode material and preparation method thereof - Google Patents
Mixed type sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a mixed type sodium ion battery anode material, which comprises O3 type lamellar sodium metal oxide and P2 type lamellar sodium metal oxide coated on the surface of the O3 type lamellar sodium metal oxide; in the XRD pattern of the mixed type sodium ion battery positive electrode material, the relation between the (002) crystal face diffraction peak intensity I (002) and the (104) crystal face diffraction peak intensity I (104) is as follows: 0.21< I (002)/I (104) <0.27, the stability of the positive electrode material is significantly improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a mixed type sodium ion battery anode material and a preparation method thereof.
Background
Although the lithium ion battery is widely applied to the fields of electric automobiles and the like, the lithium ion battery also faces some difficult problems, and is difficult to completely solve in a short period of time, for example, a plurality of side reactions exist in addition to normal charge and discharge reactions in the lithium ion battery; the lithium resource is distributed in the crust with lower content, the price is higher and higher along with the annual increase of the consumption, and the sodium resource is widely distributed in the crust and is simple and easy to obtain, so the sodium resource cost is lower.
The sodium ion battery and the lithium ion battery have similar working principles, the sodium ion battery is an important component of the low-cost high-safety energy storage facility, and the development of a stable sodium ion battery anode material is a problem to be solved urgently.
The layered oxide sodium ion battery cathode materials are generally classified into two types, P2 and O3, according to the atomic arrangement. The P2 type positive electrode material has low capacity due to low Na ion content in the material, but the material has good circulation stability, and the O3 type positive electrode material can generally provide high specific capacity due to high Na content, but Na element in the material is easy to react with water and carbon dioxide in the air due to Na-H exchange effect, so that the material stability is poor. For example, in chinese patent document CN114744179a, a sodium ion battery positive electrode material and a preparation method thereof are provided, and the provided ion battery positive electrode material is O3-layered sodium oxide, and combines a mixing mode of ultrasonic dispersion and wet grinding, and a calcination system of combination of calcination and annealing is integrated to improve uniformity of the sodium ion battery positive electrode material, however, when the positive electrode material is placed in air, sodium element is easily precipitated, resulting in surface residual alkali growth, and affecting electrochemical performance of the material.
Chinese patent document CN115148984A discloses an O3-P2 composite phase sodium ion positive electrode material, wherein the O3-P2 composite phase sodium ion positive electrode material comprises an O3 type oxide layer and a P2 type oxide layer, and the structural formula of the O3-P2 composite phase sodium ion positive electrode material is NaxMO 2 X is more than or equal to 0.8 and less than or equal to 1, M comprises Ti, V and Cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B, F; the P2 type oxide layer is generated on the surface of the O3 type oxide layer in situ to form a core-shell structure. The material has excellent specific charge and discharge capacity, excellent cycle performance, low residual alkali content on the surface and excellent comprehensive performance. However, the method needs to perform step heating calcination, and the material is cooled by an ultra-fast cooling process after calcination, so that the purpose of reducing the residual alkali content on the surface of the material can be achieved, and annealing treatment is also needed, so that the process is complex. In addition, after the material is exposed in the air, the residual alkali growth proportion of the material is too high, and the stability of the air exposure is poor.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of high residual alkali and poor exposure stability in the air of the anode material in the prior art, thereby providing the anode material of the mixed sodium ion battery and the preparation method thereof.
The invention provides a mixed type sodium ion battery anode material, which comprises O3 type lamellar sodium metal oxide and P2 type lamellar sodium metal oxide coated on the surface of the O3 type lamellar sodium metal oxide;
wherein, the chemical formula of the O3 type lamellar sodium metal oxide is as follows: naxNiaFebMncO2, a is more than or equal to 0.2 and less than or equal to 0.35,0.2, b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, and a+b+c= 1,0.8 and less than or equal to x/(a+b+c) is more than or equal to 1.08;
the chemical formula of the P2 type layered sodium metal oxide is as follows: na (Na) X MnO y In the XRD pattern of the mixed sodium ion battery positive electrode material, the relation between the (002) crystal face diffraction peak intensity I (002) and the (104) crystal face diffraction peak intensity I (104) is as follows: 0.21<I(002)/I(104)<0.27。
Further, in the mixed type sodium ion battery positive electrode material, the O3 type layered sodium metal oxide accounts for 93-91% of the mass of the mixed type sodium ion battery positive electrode material, and the P2 type layered sodium metal oxide accounts for 7-9% of the mass of the mixed type sodium ion battery positive electrode material.
Preferably, in the mixed type sodium ion battery positive electrode material, the O3 type layered sodium metal oxide accounts for 90-95% of the mass of the mixed type sodium ion battery positive electrode material, and the P2 type layered sodium metal oxide accounts for 5-10% of the mass of the mixed type sodium ion battery positive electrode material.
Further, in the XRD spectrum of the positive electrode material of the mixed sodium ion battery, the diffraction angle 2 theta 1 of the (002) crystal face is 15-17 degrees, the diffraction angle 2 theta 2 of the (102) crystal face is 39-40 degrees, the diffraction angle 2 theta 3 of the (104) crystal face is 49-50 degrees, and the diffraction angle 2 theta of the (106) crystal face is 62-63 degrees.
Further, in the XRD pattern of the positive electrode material of the mixed sodium ion battery, the (002) crystal face diffraction peak intensity I (002) is 2000-2500a.u., and the (104) crystal face diffraction peak intensity I (104) is 9000-9800a.u.
The invention also provides a preparation method of the mixed type sodium ion battery anode material, which is characterized by comprising the following steps:
s1, step: mixing a nickel source, a manganese source, an iron source and a sodium source, and then performing primary calcination;
s2, step: placing the materials after primary calcination in humid air with the humidity of 55% -75%;
s3, step: and adding the material after placing into a manganese source, and carrying out secondary calcination to obtain the mixed type sodium ion battery anode material.
Further, in the step S1, the ratio of the amounts of the substances of the metal elements in the sodium source, the nickel source, the iron source and the manganese source is 0.75-1.05:0.2-0.35:0.2-0.4:0.2-0.4, preferably: 0.9-1.0:0.28-0.33:0.30-0.35:0.30-0.40.
Further, the mass of manganese in the manganese source added in the step S2 accounts for 2-15% of the mass of the material after being placed, and is preferably 8-12%.
Further, the temperature of the primary calcination is 800-1050 ℃, preferably 900-980 ℃; the time is 6-20h; preferably 8-12h; the temperature of the secondary calcination is 400-900 ℃, preferably 600-850 ℃; the time is 5-12h; preferably 8-10h.
Further, the time of the rest in the humid air is 12-36 hours, preferably 22-26 hours.
Further, the sodium source adopted in the step S1 is sodium carbonate, the nickel source is selected from one or more of nickel oxide and nickel protoxide, and the iron source is ferric oxide; the manganese source used in step S1 or step S3 is selected from one or more of manganese oxide, manganese dioxide, manganese sesquioxide and manganese tetraoxide.
The invention also provides a sodium ion battery, which comprises any one of the mixed type sodium ion battery anode materials or the mixed type sodium ion battery anode material prepared by the preparation method of any one of the mixed type sodium ion battery anode materials.
In the invention, the battery is prepared by adopting a conventional method in the field, such as a sodium ion battery, and comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode is prepared according to the conventional technology in the field, for example, the positive electrode material, the conductive agent and the binder are prepared into slurry, and the slurry is coated on the surface of a current collector to prepare the electrode plate. The content of the positive electrode material is 90-98wt%, the content of the conductive agent is 0.2-6wt%, and the content of the binder is 0.2-6wt%. The conductive agent may be a conventional conductive agent such as SP (carbon black conductive agent), SWCNT (single-walled carbon nanotube), etc., the binder may be a conventional binder such as vinylidene fluoride PVDF, the solvent may be a conventional solvent such as N-methylpyrrolidone NMP, and the current collector is a conventional current collector such as aluminum foil. The negative electrode can be made of conventional metal sodium sheet. The electrode solution of the invention can be made of conventional commercial sodium ion electrolyte or conventional materials, for example, electrolyte comprising solvent and sodium salt, wherein the solvent is at least one selected from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate. The sodium salt is selected from sodium hexafluorophosphate and/or sodium tetrafluoroborate.
The technical scheme of the invention has the following advantages:
1. the mixed type sodium ion battery anode material provided by the invention comprises O3 type layered sodium metal oxide and P2 type layered sodium metal oxide coated on the surface of the O3 type layered sodium metal oxide; wherein, the chemical formula of the O3 type lamellar sodium metal oxide is as follows: na (Na) x Ni a Fe b Mn c O 2 A is more than or equal to 0.2 and less than or equal to 0.35,0.2, b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, a+b+c= 1,0.8 and less than or equal to x/(a+b+c) is more than or equal to 1.08; the chemical formula of the P2 type layered sodium metal oxide is as follows: na (Na) 0.7 MnO 2.05 In the XRD pattern of the mixed type sodium ion battery positive electrode material, the relation between the (002) crystal face diffraction peak intensity I (002) and the (104) crystal face diffraction peak intensity I (104) is as follows: 0.21<I(002)/I(104)<0.27。
By adding a P2 type positive electrode material protective layer on the surface of the O3 type sodium-electricity positive electrode material, the advantages of the O3 type positive electrode material and the P2 type positive electrode material (high sodium content and high capacity of the O3 type positive electrode material, stability of the P2 type positive electrode material) can be effectively combined, the defects of the O3 type positive electrode material and the P2 type positive electrode material (poor air stability of the O3 type positive electrode material and easiness in precipitation of sodium element in humid air, and low sodium content of the P2 type positive electrode material are usually low) are overcome, meanwhile, compared with the traditional transition metal oxide coating, the P2 type positive electrode material has higher conductivity, so that the conductive performance of the positive electrode material can not be basically changed by using stable positive electrode material coating, meanwhile, the air exposure stability of the material can be effectively increased, and the surface residual alkali content can be reduced.
For the mixed type sodium ion battery anode material, due to the differences of the synthesis process and conditions, the distribution of metal elements of sodium and transition metal elements is not completely uniform, so that the stability of the mixed type sodium ion battery anode material is seriously influenced, a (002) crystal face diffraction peak represents a characteristic peak of a P2 type anode material, a (104) crystal face diffraction peak represents a characteristic peak of an O3 type anode material, I (002)/I (104) represents coexistence of the P2 type anode material and the O3 type anode material to a certain extent, and the content of the P2 type anode material is smaller than that of the O3 type anode material, so that the bulk of the material is still uniform in the distribution of the O3 type anode material, and the relation between I (002) and I (104) is limited in order to ensure the stability of the anode active material: and 0.21< I (002)/I (104) <0.27, so that the residual alkali on the surface of the positive electrode material of the mixed sodium ion battery is obviously reduced, the stability of the mixed sodium ion battery exposed to air is improved, and the change rate of the residual alkali content on the surface before and after the mixed sodium ion battery is placed is reduced.
2. The mixed type sodium ion battery anode material provided by the invention can stably exist in a humid environment, and after mixed phase treatment, the electrical property of the material is not reduced, but the material is beneficial to improving the circulation stability of the material and the diffusion of sodium ions in the material.
3. The preparation method of the mixed type sodium ion battery anode material provided by the invention comprises the following steps: mixing a nickel source, a manganese source, an iron source and a sodium source, and then performing primary calcination; placing the materials after primary calcination in humid air with the humidity of 55% -75%; and adding the material after placing into a manganese source, and carrying out secondary calcination to obtain the mixed type sodium ion battery anode material. In the mixed type sodium ion battery positive electrode material prepared by the method, the mass content of the O3 type layered sodium metal oxide and the P2 type layered sodium metal oxide is proper, the obtained positive electrode material can better improve the stability of the positive electrode material, reduce the change rate of the residual alkali content before and after exposure, and has higher specific discharge capacity and better cycling stability.
4. According to the preparation method of the mixed type sodium ion battery positive electrode material, the mass of manganese in the manganese source added in the step S2 accounts for 2% -15% of the mass of the material after being placed, particularly 8% -12%, the placing time in humid air is 12-36 hours, particularly 22-26 hours, so that the stability of the positive electrode material can be better improved, the change rate of the residual alkali content before and after exposure is reduced, and the positive electrode material has higher discharge specific capacity and better cycle stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a positive electrode material and Na according to example 1 of the present invention 0.7 MnO 2.05 The upper curve is the positive electrode material of example 1, and the standard card is Na 0.7 MnO 2.05 。
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The invention provides a preparation method of a sodium ion battery anode material, which comprises the following steps:
(1) In a dry environment, weighing nickel oxide, manganese oxide, ferric oxide and sodium carbonate, and mixing in a beaker, wherein the mass ratio of the elements is sodium: nickel: iron: manganese=0.95: 0.30:0.30:0.40; carrying out primary calcination treatment on the mixed materials; the calcination temperature was 930℃and the time was 11h.
(2) Placing the materials after primary calcination in humid air with the humidity of 65% for 24 hours;
(3) And adding 15g of manganese dioxide into 100g of the material which is placed, mixing, and carrying out secondary calcination treatment at the temperature of 720 ℃ for 8 hours to obtain the final positive electrode material.
As can be seen from fig. 1, the positive electrode material for sodium ion battery of the present invention has diffraction peaks at angles 2θ of 15.8 °, 32.1 °, 39.7 °, 50.0 ° and 62.7 °. Wherein the diffraction angle 2 theta of (002) crystal face 1 Diffraction angle 2 theta of (102) crystal face of 15.8 DEG 2 Diffraction angle 2 theta of 39.7 DEG, (104) crystal face 3 The diffraction angle 2 theta 4 of the (106) crystal plane was 50.0 deg., 62.7 deg.. As can be seen from FIG. 1, the positive electrode material for sodium ion battery of the present invention contains Na 0.7 MnO 2.05 。
Example 2
The invention provides a preparation method of a sodium ion battery anode material, which comprises the following steps:
(1) In a dry environment, weighing nickel oxide, manganese oxide, ferric oxide and sodium carbonate, and mixing in a beaker, wherein the mass ratio of the elements is sodium: nickel: iron: manganese=1.0: 0.28:0.35:0.30; calcining the mixed materials; the calcination temperature was 900℃and the time was 12 hours.
(2) Placing the calcined material in humid air with the humidity of 70% for placing for 22 hours;
(3) And adding 15g of manganese dioxide into 100g of the material which is placed, mixing, and calcining at 800 ℃ for 10 hours to obtain the final positive electrode material.
Example 3
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is only different in that the rest time of the step (2) is 36h.
Example 4
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is only different in that the rest time of the step (2) is 12h.
Example 5
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is only different in that the manganese dioxide added amount in the step (3) is 23.7g, at the moment, the Mn accounts for 15%, wherein the Mn accounts for the mass percentage of manganese element in the material after being placed.
Example 6
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is different in that the manganese dioxide addition amount in the step (3) is 3.2g, and the Mn content is 2%.
Comparative example 1
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is different from the rest treatment of the step (2) only in that manganese dioxide is added into the materials after primary calcination for mixing, and secondary calcination is carried out.
Comparative example 2
The invention provides a preparation method of a positive electrode material of a sodium ion battery, which is basically the same as that of the embodiment 1, and is only different in that the material which is placed in the step (3) is directly subjected to secondary calcination without adding manganese dioxide.
Experimental example 1
XRD tests are carried out on the sodium ion battery cathode materials prepared in each example and comparative example, wherein the intensities of (002) crystal face diffraction peak intensity I (002) and (104) crystal face diffraction peak intensity I (104) are shown in the following table:
as is clear from the above table, in comparative example 2, the P2 type layered sodium metal oxide could not be formed without adding manganese dioxide, and in comparative example 1, the content of the obtained P2 type layered sodium metal oxide was small because of not being left in a humid environment, so that the intensity of the (002) crystal plane diffraction peak was low, whereas in examples 1 to 6 of the present invention, the P2 type positive electrode material protective layer was formed on the surface of the O3 type sodium electric positive electrode material, and the content of the P2 type positive electrode material protective layer was higher than that of comparative example 1.
Experimental example 2
The molecular formula and the content of the P2 type lamellar sodium metal oxide and the molecular formula and the content of the O3 type lamellar sodium metal oxide in the positive electrode materials of the sodium ion batteries prepared in each example and the comparative example are measured.
The molecular formulas of the two types of sodium metal oxides are determined as follows: the molecular formula of the P2 type layered oxide is mainly determined by XRD test, and the O3 type positive electrode material is mainly determined by the proportion of the nickel, manganese, iron and sodium sources in the primary calcination and the precipitated sodium elements after the primary calcination.
The contents of the P2 type layered sodium metal oxide and the O3 type layered sodium metal oxide in the positive electrode material of the sodium ion battery are calculated by the following method: taking example 1 as an example, measuring the residual alkali content in 100g of the material after being placed, calculating the content of precipitated sodium (free sodium) on the surface of the material after being placed according to the residual alkali content, wherein the content of free sodium is the sum of the content of sodium in sodium carbonate and the content of sodium in sodium hydroxide, calculating the content of P2 type lamellar sodium metal oxide according to the free sodium content and the molecular formula of P2 type positive electrode material, and subtracting the content of P2 type lamellar sodium metal oxide from 100% to obtain the content of O3 type lamellar sodium metal oxide.
Experimental example 3
The residual alkali content of the surfaces of the positive electrode materials prepared in each example and comparative example is tested by adopting an electrochemical titration method, the residual alkali content of the surfaces of each group of positive electrode materials is tested again after the positive electrode materials are exposed in the air for 3 days, the testing method of the residual alkali content is as follows, 1M hydrochloric acid solution is used as a titration agent, 10g of the materials to be tested are dissolved in 100ml of deionized water, after the dissolution is completed, filtration is carried out, 10g of supernatant is taken, electrochemical titration is carried out, and after two titration inflection points are displayed together, the titration is considered to be completed, and the change rate of the residual alkali content before and after the exposure is calculated.
| Residual alkali content before exposure/%) | Residual alkali content/% | Rate of change/% | |
| Example 1 | 0.76 | 0.81 | 6％ |
| Example 2 | 0.82 | 0.87 | 6％ |
| Example 3 | 1.3 | 1.5 | 15％ |
| Example 4 | 1.1 | 1.3 | 18％ |
| Example 5 | 1.0 | 1.2 | 20％ |
| Example 6 | 1.2 | 1.5 | 25％ |
| Comparative example 1 | 1.8 | 2.5 | 39％ |
| Comparative example 2 | 8 | 12.8 | 60％ |
Compared with comparative examples 1-2, the positive electrode material obtained by the invention not only can obviously reduce the residual alkali content before exposure, but also can improve the stability of the positive electrode material and reduce the change rate of the residual alkali content before and after exposure.
Experimental example 4
The positive electrode materials of the sodium ion batteries prepared in each example and comparative example are used as positive electrode active materials to prepare batteries, and the method comprises the following steps:
1. the positive electrode materials of the sodium ion batteries prepared in each example and comparative example were taken respectively, and the mass ratio of the positive electrode materials, the binder (polyvinylidene fluoride) and the conductive agent (conductive carbon black) was 92:4:4, placing the mixture in a deaeration machine, uniformly mixing, adding NMP, uniformly mixing to obtain slurry, coating the slurry on an aluminum foil, wherein the surface density is 9mg/cm 2 And obtaining a positive electrode, and then carrying out buckling assembly.
2. And (5) buckling and assembling: and (3) carrying out buckling assembly according to the sequence of a positive electrode shell (304 stainless steel), a spring plate (304 stainless steel), a gasket (304 stainless steel), a positive electrode (aluminum foil coated with a positive electrode material), a diaphragm (PE), electrolyte (containing 1mol/L sodium hexafluorophosphate, and a solvent EC (ethylene carbonate): DEC (diethyl carbonate) with a volume ratio of 3:7), a negative electrode (sodium sheet) and a negative electrode shell (304 stainless steel) to obtain the sodium ion battery.
3. The sodium ion batteries prepared in each example and comparative example were taken to have a specific capacity of 0.1C discharge and a capacity retention rate of 50 weeks at normal temperature (specifically, the method was that at normal temperature, 0.1C charge was to 4.05V,0.1C discharge was to 2V, then 1C charge was to 4.05V,1C discharge was to 2V, and 1C charge-discharge cycles were repeated 50 times to obtain capacity retention rate data.
| Project | Specific capacity for initial discharge (mAh/g) | Capacity retention/% |
| Example 1 | 153 | 98.6 |
| Example 2 | 155 | 97.9 |
| Example 3 | 149 | 96.1 |
| Example 4 | 146 | 95.6 |
| Example 5 | 146 | 96.6 |
| Example 6 | 147 | 95.8 |
| Comparative example 1 | 136 | 93.3 |
| Comparative example 2 | 127 | 90.3 |
Compared with comparative examples 1-2, the discharge specific capacity and the cycle stability of the sodium battery made of the positive electrode material are obviously improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The mixed type sodium ion battery anode material is characterized by comprising O3 type lamellar sodium metal oxide and P2 type lamellar sodium metal oxide coated on the surface of the O3 type lamellar sodium metal oxide;
wherein, the chemical formula of the O3 type lamellar sodium metal oxide is as follows: na (Na) x Ni a Fe b Mn c O 2 ，0.2≤a≤0.35，0.2≤b≤0.4，0.2≤c≤0.4，a+b+c＝1，0.8≤x/(a+b+c)≤1.08；
The chemical formula of the P2 type layered sodium metal oxide is as follows: na (Na) X MnO y In the XRD pattern of the mixed sodium ion battery positive electrode material, the relation between the (002) crystal face diffraction peak intensity I (002) and the (104) crystal face diffraction peak intensity I (104) is as follows: 0.21<I(002)/I(104)<0.27。
2. The mixed type sodium ion battery positive electrode material according to claim 1, wherein in the mixed type sodium ion battery positive electrode material, the mass percentage of the O3 type layered sodium metal oxide to the mixed type sodium ion battery positive electrode material is 90% -95%, and the mass percentage of the P2 type layered sodium metal oxide to the mixed type sodium ion battery positive electrode material is 5% -10%.
3. The mixed sodium ion battery positive electrode material according to claim 1 or 2, wherein in the XRD pattern of the mixed sodium ion battery positive electrode material, the diffraction angle 2Θ of the (002) crystal face 1 Diffraction angle 2 theta of (102) crystal face of 15-17 DEG 2 Diffraction angle 2 theta of 39-40 DEG, (104) crystal face 3 A diffraction angle 2 theta of a (106) crystal face of 49-50 DEG, and a diffraction angle 4 of 62-63 DEG; and/or, in the positive electrode material of the mixed sodium ion batteryIn the XRD pattern of the material, the (002) crystal face diffraction peak intensity I (002) is 2000-2500a.u., and the (104) crystal face diffraction peak intensity I (104) is 9000-9800a.u.
4. A method for preparing the positive electrode material of the mixed sodium ion battery as claimed in any one of claims 1 to 3, comprising the steps of:
s1, step: mixing a nickel source, a manganese source, an iron source and a sodium source, and then performing primary calcination;
s2, step: placing the materials after primary calcination in humid air with the humidity of 55% -75%;
s3, step: and adding the material after placing into a manganese source, and carrying out secondary calcination to obtain the mixed type sodium ion battery anode material.
5. The method for preparing a mixed type sodium ion battery positive electrode material according to claim 4, wherein in the step S1, the ratio of the amounts of the substances of the metal elements in the sodium source, the nickel source, the iron source and the manganese source is 0.75-1.05:0.2-0.35:0.2-0.4:0.2-0.4, preferably: 0.9-1.0:0.28-0.33:0.30-0.35:0.30-0.40.
6. The method for preparing a mixed type sodium ion battery positive electrode material according to claim 4, wherein the mass of manganese in the manganese source added in the step S2 is 2% -15%, preferably 8% -12% of the mass of the material after being placed.
7. The method for preparing a mixed type sodium ion battery positive electrode material according to any one of claims 4 to 6, wherein the sodium source adopted in the step S1 is sodium carbonate, the nickel source is one or more selected from nickel oxide and nickel protoxide, and the iron source is iron oxide; the manganese source used in step S1 or step S3 is selected from one or more of manganese oxide, manganese dioxide, manganese sesquioxide and manganese tetraoxide.
8. The method for preparing a mixed sodium ion battery positive electrode material according to any one of claims 4 to 7, wherein the temperature of the primary calcination is 800 to 1050 ℃, preferably 900 to 980 ℃; the time is 6-20h; preferably 8-12h; the temperature of the secondary calcination is 400-900 ℃, preferably 600-850 ℃; the time is 5-12h; preferably 8-10h.
9. The method for preparing a mixed sodium ion battery positive electrode material according to any one of claims 5 to 8, wherein the time of the standing in humid air is 12 to 36 hours, preferably 22 to 26 hours.
10. A sodium ion battery, characterized by comprising the mixed type sodium ion battery positive electrode material according to any one of claims 1-4 or the mixed type sodium ion battery positive electrode material prepared by the preparation method of the mixed type sodium ion battery positive electrode material according to any one of claims 5-9.
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| CN117334883A (en) * | 2023-11-24 | 2024-01-02 | 广东省中科海钠科技有限责任公司 | Sodium-electricity positive electrode material and preparation method thereof |
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2022
- 2022-12-30 CN CN202211734222.7A patent/CN116014119A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117334883A (en) * | 2023-11-24 | 2024-01-02 | 广东省中科海钠科技有限责任公司 | Sodium-electricity positive electrode material and preparation method thereof |
| CN117334883B (en) * | 2023-11-24 | 2024-02-02 | 广东省中科海钠科技有限责任公司 | Sodium-electricity positive electrode material and preparation method thereof |
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