CN117638051A - Coated O3 type manganese-based sodium ion battery positive electrode material and preparation method thereof - Google Patents

Coated O3 type manganese-based sodium ion battery positive electrode material and preparation method thereof Download PDF

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CN117638051A
CN117638051A CN202311860174.0A CN202311860174A CN117638051A CN 117638051 A CN117638051 A CN 117638051A CN 202311860174 A CN202311860174 A CN 202311860174A CN 117638051 A CN117638051 A CN 117638051A
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ion battery
sodium
sodium ion
phosphate
type manganese
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CN117638051B (en
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刘城位
简健明
范江
万国江
陈林安
张晋江
司徒健文
梁小婷
刘泽华
黄凤怡
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Jiangmen Kanhoo Industry Co ltd
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    • 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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Abstract

The invention belongs to the technical field of sodium ion batteries, and discloses a coated O3 type manganese-based sodium ion battery anode material and a preparation method thereof, wherein the coated O3 type manganese-based sodium ion battery anode material comprises an O3 type manganese-based sodium ion battery anode material and sodium titanium phosphate coated on the surface of the O3 type manganese-based sodium ion battery anode material; the sodium source forming the sodium titanium phosphate is the residual alkali on the surface of the O3-type manganese-based sodium ion battery anode material; the molar quantity of the sodium titanium phosphate is 0.6 to 0.8 times of the molar quantity of sodium ions in the surface residual alkali. The invention uses residual alkali on the surface of the O3-based manganese-based sodium ion battery anode material as a sodium source, and prepares the phosphate and the titanium source with specific dosage ranges to generate the titanium sodium phosphate coating, thereby effectively avoiding the influence of the residual alkali on the performance of the anode material and further improving the performance of the anode material through the titanium sodium phosphate coating.

Description

Coated O3 type manganese-based sodium ion battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a coated O3 type manganese-based sodium ion battery anode material and a preparation method thereof.
Background
In recent years, a series of positive and negative electrode materials for sodium ion batteries have been researched and developed, and a new development direction has been developed.
The positive electrode material of the sodium ion battery is a key material of the sodium ion battery, and three positive electrode materials which are currently mainstream are transition metal layered oxide, prussian blue analogues and polyanion compounds respectively; the O3 type manganese-based layered oxide sodium ion battery anode material has the advantages of relatively low cost, high capacity and high energy density, and has great application prospect; however, some defects affect the practical application, the spacing between layers of the O3 type positive electrode material is large, the material is extremely sensitive to moisture in air, capacity loss often occurs in the material storage process, and the application of the O3 type manganese-based layered oxide sodium ion battery positive electrode material is limited.
At present, electrochemical performance of a material is improved mainly by means of surface modification, metal doping substituted by chemical activity or inert elements, improving a preparation process (morphology and crystal structure) and the like, wherein a layer of material is coated on the surface of a positive electrode material, which is a main means of surface modification.
As in prior art 1: chinese patent application 202211595253.9 discloses a Na 2 MnPO 4 F-coated O3 type layered sodium ion battery anode material and preparation method thereof, in particular to Na with monoclinic structure 2 MnPO 4 F-coated O3-shaped layered sodium ion battery anode material NaNixM 1 -x-yMnyO 2 Wherein M is one or more of Co, fe, mg, ti, cu, al and the like.
The method adopts a hydrothermal method to coat Na on the surface of the O3 type layered sodium ion battery anode material 2 MnPO 4 F, the coating layer prevents adverse effects caused by side reactions caused by decomposition of the high-voltage electrolyte, improves the air stability of the material, and inhibits the surface of the material and H 2 O and CO 2 The cycling stability and the multiplying power performance of the O3 type layered sodium ion battery anode material are improved; however, due to the adoption of wet coating, a large amount of residual alkali is generated on the surface of the O3 type layered sodium ion battery anode material in the coating process, so that the battery performance of the anode material is reduced.
Therefore, the O3-shaped layered sodium ion battery positive electrode material needs to be coated by considering other coating modes, and based on the coating, the sodium titanium phosphate NaTi 2 (PO 4 ) 3 The Nasicon has an open three-dimensional framework and rapid ion diffusion rate, is mainly used for solid electrolyte and sodium-electricity negative electrode, is an ideal coating material in the field of positive electrode materials, and has few sodium titanium phosphate surface modified sodium-electricity positive electrode materials in the literature.
Therefore, the surface of the O3 type manganese-based layered oxide sodium ion battery positive electrode material is coated with the sodium titanium phosphate, so that the direct contact of the O3 type manganese-based layered oxide sodium ion battery positive electrode material with air can be prevented under the condition that the capacity of the positive electrode material is not affected, the air stability of the material is improved, meanwhile, the protective layer can reduce the direct contact of the material with electrolyte, side reactions are reduced, irreversible phase transformation of the material is restrained, and the air stability and the circulation stability of the material are finally improved.
Wherein prior art 2: chinese patent application 202310786687.5 discloses a positive electrode material, a method for preparing the same and a sodium ion battery, the positive electrode material comprising: the oxide coating comprises a layered O3 type oxide and a coating layer coated on the surface of the layered O3 type oxide, wherein the coating layer comprises sodium titanium phosphate and/or metal doped sodium titanium phosphate.
According to the technical scheme of the patent application, the titanium sodium phosphate coating layer is coated on the surface of the layered O3 oxide by adopting the sintering means to form the anode material, so that the problem of a large amount of residual alkali caused by wet coating can be effectively avoided, but part of sodium ions spontaneously deviate from the solution to form the residual alkali during high-temperature sintering, so that the problem of performance degradation of the anode material caused by the residual alkali is not effectively solved although the residual alkali is effectively controlled by adopting the technical scheme of the patent application.
Prior art 3: chinese patent 202211251801.6 discloses a sodium ion battery anode material, a preparation method and application thereof, wherein the sodium ion battery anode material comprises an inner core and a coating layer coated on at least part of the surface of the inner core; the core includes Na x (Ni y Fe z Mn w L 1-y-z-w )O 2+δ Wherein L is at least one of Cu, li, zn, al, mg, ti, zr, sr, sb, nb, mo, Y or W, x is more than or equal to 0.8 and less than or equal to 1.1,0.1 and y is more than or equal to 0.45,0.15 and less than or equal to 0.5,0.4 and less than or equal to W and less than or equal to 0.75,0.65 and less than or equal to y+z+w is more than or equal to 1, and delta is more than or equal to 0.02 and less than or equal to 0.02. The coating layer comprises Na 1+m MM’Si m P 3 -mO 12 Wherein M or M' is independently selected from at least one of Fe, V, ti, zr, al, sc, mn, la, nb and In, and M is more than or equal to 0 and less than or equal to 3.
The above patent specification discloses that residual alkali overflowed from the core material can be used as sodium source, and then coated with Na 1+ m MM’Si m P 3 -mO 12 The layer can effectively solve the problem of performance degradation of the anode material caused by residual alkali; however, when the sodium ion positive electrode material is coated with the sodium titanium phosphate coating layer according to the scheme, the performance improvement effect of the positive electrode material is not obvious, and the titanium phosphate coating layer is lackSodium is an ideal coating layer material to exert the most effective preparation scheme of the sodium ion battery anode material.
Disclosure of Invention
One of the purposes of the invention is to provide a coated O3 type manganese-based sodium ion battery anode material, so as to solve the problem that the prior art does not achieve the ideal performance improvement effect by using residual alkali as a sodium source of a coating layer to coat sodium titanium phosphate.
The invention further aims to provide a preparation method of the coated O3 type manganese-based sodium ion battery positive electrode material, residual alkali on the surface of the O3 type manganese-based sodium ion battery positive electrode material is fully utilized to combine with a titanium source and phosphate to form a specific amount of titanium sodium phosphate coating layer, so that the performance influence caused by the residual alkali is effectively reduced, and meanwhile, the electrical property of the positive electrode material can be further improved through the coating layer.
In order to achieve the above purpose, the invention provides a coated O3 type manganese-based sodium ion battery anode material, wherein the coated O3 type manganese-based sodium ion battery anode material comprises an O3 type manganese-based sodium ion battery anode material and sodium titanium phosphate coated on the surface of the O3 type manganese-based sodium ion battery anode material;
the sodium source forming the sodium titanium phosphate is the residual alkali on the surface of the O3-type manganese-based sodium ion battery anode material; the molar quantity of the sodium titanium phosphate is 0.6 to 0.8 times of the molar quantity of sodium ions in the surface residual alkali.
Preferably, the sodium titanium phosphate is generated from phosphate, a titanium source, and a sodium source.
Further, the phosphate comprises at least one of monoammonium phosphate and diammonium phosphate.
Further, the titanium source comprises at least one of an oxide, a hydroxide, and tetrabutyl titanate of titanium.
Preferably, the O3-type manganese-based sodium ion battery positive electrode material is Na x (NiFeMn) 1/3*(1-a) M a O 2 Wherein x and a are mole numbers, x is more than 0.92 and less than 1.04,0.01 and less than or equal toa is less than or equal to 0.1, M is one or more of metal ions Ca, mg, zn, al, Y, ti, zr, nb and Mo, and the chemical formula of the sodium titanium phosphate layer is NaTi 2 (PO 4 ) 3 。
The invention also discloses a preparation method of the coated O3 type manganese-based sodium ion battery anode material, which comprises the following steps:
step 1: sintering to obtain an O3-type manganese-based sodium ion battery anode material;
step 2: measuring the residual alkali amount on the outer surface of the O3 type manganese-based sodium ion battery anode material, weighing the amount of phosphate and titanium source to be added, and uniformly mixing the phosphate and the titanium source with the O3 type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: and (3) sintering the mixed material obtained in the step (2) under the air or oxygen atmosphere, heating to 820-920 ℃ at the heating rate of 1-5 ℃/min, and preserving heat for 4-10h to obtain the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate.
Preferably, the O3-type manganese-based sodium ion battery anode material is prepared by the following method: will 0.5mol Na 2 CO 3 、0.96mol Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 、0.04mol TiO 2 Uniformly mixing, heating to 980-1050 ℃ at a heating rate of 1-5 ℃/min under the air or oxygen atmosphere, and preserving heat for 10-18h.
Advantageous effects
Compared with the prior art, the invention has at least the following advantages:
(1) According to the invention, residual alkali on the surface of the anode material of the O3-based manganese-based sodium ion battery is used as a sodium source, and phosphate and a titanium source with specific dosage ranges are configured to generate the titanium sodium phosphate coating, so that the influence of the residual alkali on the performance of the anode material is effectively avoided, and the performance of the anode material is further improved through the titanium sodium phosphate coating;
(2) According to the invention, the residual alkali on the surface of the O3-based manganese-based sodium ion battery anode material is used as a sodium source, so that the amount of the titanium sodium phosphate coating layer is effectively controlled, the molar amount of the titanium sodium phosphate is 0.6-0.8 times of the molar amount of sodium ions in the residual alkali on the surface, and the problem that the titanium sodium phosphate can generate negative effects under the condition of excessive residual alkali is effectively avoided; the residual alkali can be effectively and fully utilized, the multiplying power performance and the cycle performance of the positive electrode material can be effectively improved, and the situation that excessive phosphate and titanium sources rob sodium ions in the internal structure of the positive electrode material to cause performance degradation is avoided;
(3) The anode material obtained by the invention has the advantages of good multiplying power performance and good cycle performance.
Drawings
The invention is further described below with reference to the drawings and examples;
FIG. 1 is an SEM image of an O3 type manganese-based sodium ion battery positive electrode material (uncoated);
FIG. 2 is an SEM image of a coated O3-type manganese-based sodium-ion battery anode material of example 1 of the present invention;
Detailed Description
The invention is further described below in connection with the examples, which are not to be construed as limiting the invention in any way, but rather as a limited number of modifications which are within the scope of the appended claims.
In order to explain the technical content of the present invention in detail, the following description will further explain the embodiments.
The O3 type manganese-based sodium ion battery positive electrode material of the invention can be obtained by sintering in the prior art, and in the following examples and comparative examples, the O3 type manganese-based sodium ion battery positive electrode material is NaNi 0.32 Fe 0.32 Mn 0.32 Ti 0.04 O 2 The method is obtained by sintering the following steps:
will 0.5mol Na 2 CO 3 、0.96mol Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 、0.04mol TiO 2 Uniformly mixing, heating to 1000 ℃ at a heating rate of 5 ℃/min under the air or oxygen atmosphere, and preserving heat for 15h.
Based on the total content of residual alkali on the surface of the material, sodium carbonate and sodium hydroxide are the most main components of the residual alkali, the method for testing the residual alkali on the surface of the positive electrode material comprises the following steps: testing the carbon content of the surface of the material by using a carbon-sulfur analyzer, and converting to obtain the content of sodium carbonate on the surface; and obtaining the sodium hydroxide content on the surface of the material by an acid-base titration method, and finally adding the sodium hydroxide content and the sodium hydroxide content to obtain the surface sodium molar quantity.
Example 1
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.02184mol of titanium dioxide and 0.03276mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 in an air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with sodium titanium phosphate;
the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate is 0.6 times of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Example 2
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.02912mol of titanium dioxide and 0.04368mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 920 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain the O3-type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate;
the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate is 0.8 times of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Example 3
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.02548mol of titanium dioxide and 0.03822mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 850 ℃ at a heating rate of 5 ℃/min, and preserving heat for 7 hours to obtain the O3-type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate;
the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate is 0.7 times of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Example 4
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.02912mol of titanium dioxide and 0.04368mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain the O3-type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate;
the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate is 0.9 times of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Comparative example 1
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.00546mol of sodium carbonate, 0.02184mol of titanium dioxide and 0.03276mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 in an air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with sodium titanium phosphate;
the sodium source is added in the comparative example, and the coating amount of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated by the sodium titanium phosphate is 0.6 times of that of residual alkali.
Comparative example 2
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.0091mol of sodium carbonate, 0.0364mol of titanium dioxide and 0.0546mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 in an air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with sodium titanium phosphate;
the sodium source is added in the comparative example, and the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated by the sodium titanium phosphate is 1 time of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Comparative example 3
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain an O3-type manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the positive electrode material of the O3-based sodium ion battery per 60g is measured to be 0.0182mol Na + Weighing 0.04368mol of titanium dioxide and 0.06552mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with sodium titanium phosphate;
the comparative example adopts a titanium source with 2.4 times mole of sodium ions in residual alkali on the surface of the O3-type manganese-based sodium ion battery anode material and a phosphoric acid source with 3.6 times mole of sodium ions in residual alkali on the surface of the O3-type manganese-based sodium ion battery anode material to coat the O3-type manganese-based sodium ion battery anode material.
Comparative example 4
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.0364mol of titanium dioxide and 0.0546mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with sodium titanium phosphate;
the molar quantity of the sodium titanium phosphate of the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate is 1 time of the molar quantity of sodium ions in residual alkali on the surface of the O3 type manganese-based sodium ion battery anode material.
Comparative example 5
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.0182mol of zirconium dioxide, 0.0182mol of titanium dioxide and 0.0546mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with zirconium titanium sodium phosphate;
the comparative example adopts dry coating, and the O3 type manganese-based sodium ion battery anode material coated by zirconium titanium sodium phosphate is NaTiZr (PO) 4 ) 3 The molar quantity is 1 time of the molar quantity of sodium ions in residual alkali on the surface of the O3-based manganese-based sodium ion battery anode material.
Comparative example 6
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.01092mol of zirconium dioxide, 0.01092mol of titanium dioxide and 0.03276mol of ammonium dihydrogen phosphate, and uniformly mixing with the O3-type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: sintering the mixed material obtained in the step 2 in an air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain an O3 type manganese-based sodium ion battery anode material coated with zirconium titanium sodium phosphate;
the comparative example adopts dry coating, and the O3 type manganese-based sodium ion battery anode material coated by zirconium titanium sodium phosphate is NaTiZr (PO) 4 ) 3 O3-type manganese-based sodium ion battery anodeAnd 0.6 times of the molar quantity of sodium ions in the residual alkali on the surface of the material.
Comparative example 7
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + Weighing 0.01092mol of zirconium nitrate, 0.01092mol of tetrabutyl titanate and 0.03276mol of ammonium dihydrogen phosphate, dissolving the anode material of the O3-based manganese-based sodium ion battery in ethanol, uniformly mixing to obtain a mixed liquid phase, stirring and evaporating the mixed liquid phase at 80 ℃, and then drying in an oven for 12 hours to obtain a mixed system;
step 3: sintering the mixed system obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 8 hours to obtain the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate;
the comparative example adopts wet coating, and the O3 type manganese-based sodium ion battery anode material coated by zirconium titanium sodium phosphate is NaTiZr (PO) 4 ) 3 The molar quantity is 0.6 times of the molar quantity of sodium ions in residual alkali on the surface of the O3-based manganese-based sodium ion battery anode material.
Comparative example 8
The coated O3 type manganese-based sodium ion battery positive electrode material is prepared by the following steps:
step 1: sintering to obtain 60g of O3-based manganese-based sodium ion battery anode material;
step 2: the residual alkali content of the outer surface of the O3-based manganese-based sodium ion battery anode material is measured to be 0.0182mol Na + 0.0182mol of zirconium nitrate, 0.0182mol of tetrabutyl titanate and 0.0546mol of ammonium dihydrogen phosphate are weighed and dissolved in ethanol, and are uniformly mixed to obtain a mixed liquid phase, the mixed liquid phase is stirred and evaporated to dryness at 80 ℃, and then the mixed liquid phase is dried in an oven for 12 hours to obtain a mixed system;
step 3: sintering the mixed system obtained in the step 2 under the air atmosphere, heating to 820 ℃ at a heating rate of 5 ℃/min, and preserving heat for 8 hours to obtain the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate;
the comparative example adopts wet coating, and the O3 type manganese-based sodium ion battery anode material coated by zirconium titanium sodium phosphate is NaTiZr (PO) 4 ) 3 The molar quantity is 1 time of the molar quantity of sodium ions in residual alkali on the surface of the O3-based manganese-based sodium ion battery anode material.
Performance testing
(1) Surface residual alkali test
Characterization of carbonate and hydroxide on the surface of the positive electrode materials obtained in examples 1-4 and comparative examples 1-8 by using a carbon-sulfur analyzer and an acid-base titration method is shown in Table 1;
TABLE 1 results of residual alkali test on the surfaces of the cathode materials obtained in examples 1 to 4 and comparative examples 1 to 8
From the data in table 1, it can be seen that:
as can be seen from examples 1-4 and comparative example 3, as the titanium dioxide and monoammonium phosphate increase, the residual alkali of the two-burned material gradually decreases; example 2 and example 4 are compared, the addition amounts of the two are the same, but the residual alkali in example 2 is slightly higher than that in example 4 because the temperature has a slight influence on the residual alkali content, sodium ions are spontaneously released during sintering, and the sintering temperature of example 2 is higher and the sodium ion release amount is larger in relation to the temperature.
Sodium carbonate is additionally added as a sodium source, a titanium source and phosphate to form a titanium sodium phosphate coating layer in comparative examples 1 and 2, but part of titanium dioxide enters crystal lattices and part of phosphate volatilizes during sintering, so that excessive sodium ions are caused, and residual alkali is increased; by the technical scheme of using the residual alkali as a sodium source, the residual alkali amount of the positive electrode material can be effectively reduced, and the residual alkali can be used for forming the titanium sodium phosphate coating layer to improve the battery performance of the positive electrode material.
As can be seen from examples 1, 4 and 5, the use of residual alkali as sodium source can effectively reduce the residual alkali content of the final positive electrode material by using 1-fold residual alkali as sodium source compared with the use of 0.6-fold residual alkali as sodium source; but the performance is not yet known.
Similarly, as is clear from the comparison between comparative example 6 and example 1, the same amount of residual alkali was used as the sodium source for the coating layer coating, and the material selection of the coating layer was not related to the amount of residual alkali in the final positive electrode material.
As is clear from the comparison of the data of comparative examples 7 and 6, the amount of residual alkali produced by the liquid phase coating and the solid phase coating was changed, the composition of residual alkali was also changed, and the liquid phase coating resulted in an increase in NaOH content and Na content 2 CO 3 The content is reduced.
As can be seen from the comparison of the data of comparative examples 7 and 8, the use of residual alkali as sodium source for coating layer coating, and the use of residual alkali in an amount of 1 time as sodium source, compared with the use of residual alkali in an amount of 0.6 time as sodium source, can effectively reduce the residual alkali amount of the final positive electrode material.
(2) Testing of electrical properties
The positive electrode materials obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to electrochemical performance characterization using a battery test cabinet, and the results are shown in table 2;
TABLE 2 results of the battery cell performance tests of examples 1-5 and comparative examples 1-3
As can be seen from table 2:
as can be seen from the data of examples 1 to 4, the super-ionic conductor NaTi is generated due to the surface 2 (PO4) 3 The discharge specific capacity of 0.1C in the slightly sacrificed part greatly improves the 1C rate performance and the 1C100 cycle retention rate of the material.
As is clear from the comparison of the data of examples 1 to 4 and comparative example 4, although comparative example 4 uses residual alkali sufficiently, the coating layer is too thick, which results in deterioration of the rate performance and cycle performance, and further sacrifices the specific discharge capacity of 0.1C, and it is shown that the preferred embodiment of the present invention is that the molar amount of sodium titanium phosphate of the coating layer is 0.6 to 0.8 times the molar amount of sodium ions in the residual alkali on the surface.
While the technical scheme that the sodium source, the phosphate and the titanium source are additionally added in the comparative examples 1 and 2 to form the titanium sodium phosphate coating layer effectively improves the multiplying power performance and the cycle performance of the positive electrode material through the titanium sodium phosphate coating layer, according to the table 1, as the residual alkali on the surface of the positive electrode material obtained in the comparative examples 1 and 2 is too much and the residual alkali inert layer is too thick, the multiplying power performance and the cycle performance of the finally obtained positive electrode material are not greatly improved, but the 0.1C discharge specific capacity of the positive electrode material is greatly sacrificed; as can be seen from the comparison of the data of example 1 and comparative examples 1, 4 and 2, the formation of the sodium titanium phosphate coating layer using a part of residual alkali as a sodium source can effectively improve the rate performance and cycle performance of the positive electrode material and avoid the great decrease of the capacity of the positive electrode material, and simultaneously effectively avoid the problem of residual alkali lifting caused by the formation of the coating layer by secondary sintering.
Meanwhile, as can be seen from the data gap between example 1 and comparative examples 1, 4 and 2, example 1 uses sodium ions with a molar quantity of 0.6 times that of the residual alkali on the surface of the positive electrode material as a sodium source of the titanium sodium phosphate coating layer, while comparative example 1 additionally adds sodium carbonate as a new sodium source to form a sodium source of the titanium sodium phosphate coating layer, the performance gap between example 1 and comparative example 1 is obvious because the additional sodium source added in comparative example 1 forms new residual alkali during sintering to affect the performance of the positive electrode material; the difference between the performance of the solution of adding additional sodium source, titanium source and phosphate to form an excessively thick coating layer and the performance of the solution of using residual alkali, titanium source and phosphate to form an excessively thick coating layer in comparative example 4 are relatively small, that is, the performance degradation effect of the sodium source of the sodium titanium phosphate coating layer using 1 time mole amount of residual alkali on the surface of the positive electrode material in comparative example 4 is more obvious compared with that in example 1, and the possible reasons are that: comparative example 4 excessive titanium source and phosphate not only use residual alkali as sodium source when sintering to form a titanium sodium phosphate coating layer, but also possibly rob part of sodium ions in the internal structure of the positive electrode material, so that the internal structure of the positive electrode material is damaged to cause performance degradation, while comparative example 2 adds additional sodium source and although residual alkali is added and an excessively thick coating layer is formed, the possibility that the phosphate and the titanium source rob part of sodium ions in the internal structure of the positive electrode material is very little in the sintering process due to the additional sodium source and residual alkali serving as the sodium source of titanium sodium phosphate, so that the integrity of the internal structure of the positive electrode material is ensured, and performance degradation is mainly represented by residual alkali brought by the additional sodium source and is not damage to the internal structure of the positive electrode material;
from this, it is found that the solution of comparative example 4 is intended to fully utilize the residual alkali on the surface of the positive electrode material, but the problem arises that the internal structure of the positive electrode material is robbed to damage sodium ions, and on the contrary, a new problem of performance degradation arises.
As is clear from the data of comparative example 3 in table 1, the formation of the coating layer using an excessive amount of titanium source and phosphate greatly reduced the residual alkali content of the positive electrode material, but as is clear from the data in table 2, comparative example 3 effectively forms the sodium titanium phosphate coating layer, but since the titanium source and phosphate are excessive, the sodium ions in the positive electrode material are largely robbed to form a thick sodium titanium phosphate coating layer, the internal structure of the positive electrode material is seriously damaged, and the overall performance of the positive electrode material is greatly reduced.
From the comparison of the data of comparative examples 5 and 6, comparative examples 7 and 8, it is understood that the thickness of the coating layer and the electrical properties of the positive electrode material of sodium ion battery are positively correlated for the non-sodium titanium phosphate coating layer, and the difference is caused by the fact that the titanium sodium phosphate coating layer is used in the present invention of example 1 and comparative example 4, which is: zr element makes the coating layer have aggregation effect, so that the contact surface between the coating layer and the material is reduced, when the coating amount is low, the generated coating layer can not completely wrap the material, the effect is not achieved, the surface stress of particles is increased, the performance is deteriorated, and when the coating layer is increased to a certain amount, the coating layer can completely wrap the positive electrode material, so that the coating effect can be exerted.
And according to the comparison of the data of the example 1 and the comparative examples 5-8, the improved performance effect of the titanium sodium phosphate coating layer is better, which shows that the titanium sodium phosphate is a more ideal coating layer material.
As is clear from the comparison of the data of comparative examples 6 and 7, the liquid phase coating and the solid phase coating are different from each other, but the difference in performance is only a small difference due to the coating means, and no significant difference occurs.
Therefore, the invention adopts the sodium ion with the molar quantity of 0.6 to 0.8 times in the surface residual alkali as the sodium source of the titanium sodium phosphate coating layer, and can obviously improve the multiplying power performance and the cycle performance of the positive electrode material.
Meanwhile, as can be seen from SEM images of fig. 1 and 2, the gully before the O3 type manganese-based sodium ion battery positive electrode material is not coated is obvious, while the gully after the titanium sodium phosphate coating layer is coated by the invention is blurred, so that the titanium sodium phosphate of the invention is uniformly coated on the surface of the O3 type manganese-based sodium ion battery positive electrode material to form the coated O3 type manganese-based sodium ion battery positive electrode material.
The embodiments presented herein are merely implementations selected from combinations of all possible embodiments. The following claims should not be limited to the description of the embodiments of the invention. Some numerical ranges used in the claims include sub-ranges within which variations in these ranges are also intended to be covered by the appended claims.

Claims (6)

1. The coated O3 type manganese-based sodium ion battery positive electrode material is characterized by comprising an O3 type manganese-based sodium ion battery positive electrode material and sodium titanium phosphate coated on the surface of the O3 type manganese-based sodium ion battery positive electrode material;
the sodium source forming the sodium titanium phosphate is the residual alkali on the surface of the O3-type manganese-based sodium ion battery anode material; the molar quantity of the sodium titanium phosphate is 0.6 to 0.8 times of the molar quantity of sodium ions in the surface residual alkali.
2. The coated O3 type manganese-based sodium ion battery positive electrode material according to claim 1, wherein the sodium titanium phosphate is generated from a phosphate, a titanium source, and a sodium source.
3. The coated O3 type manganese-based sodium ion battery positive electrode material according to claim 2, wherein the phosphate comprises one of monoammonium phosphate and diammonium phosphate.
4. The coated O3 type manganese-based sodium ion battery positive electrode material according to claim 2, wherein the titanium source comprises at least one of an oxide, a hydroxide, and tetrabutyl titanate of titanium.
5. The sodium titanium phosphate coated O3 type manganese-based sodium ion battery positive electrode material according to claim 1, wherein the O3 type manganese-based sodium ion battery positive electrode material is Na x (NiFeMn) 1/3*(1-a) M a O 2 Wherein x and a are molar numbers, x is more than 0.92 and less than 1.04,0.01 and less than or equal to a and less than or equal to 0.1, M is one or more of metal ions Ca, mg, zn, al, Y, ti, zr, nb and Mo, and the chemical formula of the sodium titanium phosphate layer is NaTi 2 (PO 4 ) 3 。
6. A method for preparing the coated O3 type manganese-based sodium ion battery positive electrode material according to any one of claims 1 to 5, comprising the steps of:
step 1: sintering to obtain an O3-type manganese-based sodium ion battery anode material;
step 2: measuring the residual alkali amount on the outer surface of the O3 type manganese-based sodium ion battery anode material, weighing the amount of phosphate and titanium source to be added, and uniformly mixing the phosphate and the titanium source with the O3 type manganese-based sodium ion battery anode material to obtain a mixed material;
step 3: and (3) sintering the mixed material obtained in the step (2) under the air or oxygen atmosphere, heating to 820-920 ℃ at the heating rate of 1-5 ℃/min, and preserving heat for 4-10h to obtain the O3 type manganese-based sodium ion battery anode material coated with the sodium titanium phosphate.
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