CN116525813B - Layered oxide, preparation method thereof and sodium ion battery positive electrode plate - Google Patents

Layered oxide, preparation method thereof and sodium ion battery positive electrode plate Download PDF

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CN116525813B
CN116525813B CN202310759926.8A CN202310759926A CN116525813B CN 116525813 B CN116525813 B CN 116525813B CN 202310759926 A CN202310759926 A CN 202310759926A CN 116525813 B CN116525813 B CN 116525813B
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sodium
sintering
layered oxide
layer material
oxide
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CN116525813A (en
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薛志高
武增雪
孙伟丽
王尊志
刘瑞
李琮熙
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Ningbo Ronbay Lithium Battery Material Co Ltd
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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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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 provides a layered oxide and a preparation method thereof, and a sodium ion battery positive electrode plate, wherein the layered oxide comprises a core layer material and a shell layer material coated on at least part of the surface of the core layer material; wherein the core layer material is ternary sodium-rich layered oxide, and the shell layer material is quaternary sodium-rich layered oxide; thickness D of core material 1 Thickness D with layered oxide 0 Satisfy D of 0.4-0 1 /D 0 Less than or equal to 0.8; average value L of sodium ion interlayer spacing in shell material 1 Average value L of interlayer spacing with sodium ions in core layer material 2 The following relationship is satisfied: 0 a < L 1 ‑L 2 And less than or equal to 0.2A. In the layered oxide provided by the invention, the interlayer spacing of sodium ions of the shell layer material is larger than that of the core layer material, so that the deintercalation of sodium ions is facilitated, and the influence on the stability of the material due to accumulation is avoided.

Description

Layered oxide, preparation method thereof and sodium ion battery positive electrode plate
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a layered oxide, a preparation method thereof and a positive plate of a sodium ion battery.
Background
The sodium ion battery is a battery which realizes charge and discharge by utilizing the process of inserting and extracting sodium ions between the anode and the cathode. During charging, na ＋ The negative electrode is embedded into the electrolyte after the positive electrode is separated from the negative electrode, and meanwhile, the compensation charge of electrons is supplied to the negative electrode through an external circuit, so that the charge balance of the positive electrode and the negative electrode is ensured. On the contrary, na ＋ The positive electrode is inserted into the negative electrode through the electrolyte. Under normal charge and discharge conditions, intercalation and deintercalation of sodium ions between the anode and the cathode does not destroy the basic chemical structure of the electrode material.
The sodium-rich layered oxide is used for a positive electrode material of a sodium ion battery, and in the sodium-rich layered oxide, a smaller sodium ion interlayer distance endows more active sodium content in a bulk phase, but can limit the deintercalation of sodium ions, and particularly, the stacking and blocking are easy to cause in the long-term deintercalation process, so that the stability of the material is influenced.
Disclosure of Invention
In view of the above, the present invention provides a layered oxide, which includes a core material and a shell material coated on at least a portion of the surface of the core material; wherein the core layer material comprises ternary sodium-rich layered oxide, and the shell layer material comprises quaternary sodium-rich layered oxide; diameter D of core material 1 Diameter D with layered oxide 0 Satisfy D of 0.4-0 1 /D 0 Less than or equal to 0.8; average value L of sodium ion interlayer spacing in shell material 1 Average value L of interlayer spacing with sodium ions in core layer material 2 The following relationship is satisfied: 0. a < L 1 -L 2 ≤0.2Å。
Based on the related technology, the smaller sodium ion interlayer spacing can contain more active sodium, but can limit the deintercalation of sodium ions, while the larger sodium ion interlayer spacing is beneficial to the deintercalation of sodium ions but cannot contain more active sodium; the present invention provides a layered oxide in which the interlayer spacing of sodium ions is in a state of being changed. Ternary sodium-rich layered oxides typically have smaller sodium interlayer spacing than quaternary sodium-rich layered oxides due to the reduced repulsive force between oxygen and oxygen caused by the high entropy system slowing down electron localization between transition metal layers. Thus, a layered oxide is designed comprising a core material and a shell material; wherein the core layer material is ternary sodium-rich layered oxide, namely oxide containing three elements, and sodium ions can be contained between layers of the oxide; the shell material is quaternary sodium-rich layered oxide, and further comprises doping elements on the basis of ternary.
The layered oxide is generally in the shape of an irregular single crystal, so as to realize smooth deintercalation of sodium ions and ensure the content of the sodium ions; preferably, the layered oxide satisfies the following two conditions. First, in the thickness direction of the layered oxide, the core layer material occupies 40-80%; the shell material occupies 20 to 60 percent. Specifically, the particle size of the sodium-rich layered oxide is 5-12 μm; the particle size of the core material is 2-10 μm, preferably 4.5 μm; the thickness of the shell material is 1-8. Mu.m, preferably 1.5. Mu.m. Secondly, the average value of the sodium ion interlayer spacing in the shell layer material is larger, so in the technical scheme, the core layer material has smaller sodium ion interlayer spacing and can contain more active sodium; the shell material has larger interlayer spacing of sodium ions, and is favorable for the deintercalation of sodium ions.
Further, the sodium ion layer spacing in the shell material gradually increases along the direction from the core material to the shell material.
In the technical scheme, the interlayer spacing of the sodium ions of the shell material is gradually increased from inside to outside, and the effect of ensuring the sodium ion deintercalation stability while ensuring the sufficient active sodium content of the layered oxide can be realized as a preferable scheme.
Further, the sodium layer change rate K of the layered oxide d The numerical ranges of (2) are as follows: k is more than 0 d ≤10 -3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein K is d The calculation mode of (2) is as follows: k (K) d = ( L 1 - L 2 )/D 2 ；L 1 Is the average value of the interlayer spacing of sodium ions in the shell material; l (L) 2 Is the average value of the interlayer spacing of sodium ions in the core layer material; d (D) 2 Is the thickness of the shell material.
In the technical proposal, the EDS scanning is carried out on the section of the layered oxide, so that the size of the core layer material and the shell layer material and the change rate K of the sodium layer can be effectively quantified d The reaction is that the sodium ion interlayer spacing of the shell layer material changes more relative to the core layer material, and the larger the numerical value is, the larger the sodium ion interlayer spacing of the shell layer material changes relative to the core layer material; the deintercalation of sodium ions is more facilitated.
Further, the composition of the core layer material is shown as a formula (I):
Na b Ni c Fe d Mn e O g (Ⅰ)；
wherein b is more than or equal to 0.67 and less than or equal to 1.25,0.15, c is more than or equal to 0.35,0.15, d is more than or equal to 0.35,0.25 and less than or equal to e is more than or equal to 0.66, and c+d+e= 1,1.75 and g is more than or equal to 2.25; the algebraic sum of the positive and negative valencies of Na, ni, fe, mn, O in formula (I) is 0.
In the technical scheme, nickel, iron and manganese are used as base materials, and the prepared anode material has better conductivity and higher theoretical capacity and conductivity; the synthesis process is simpler, and large-scale production, research and popularization can be realized.
Further, the composition of the shell material is shown as a formula (II):
Na b1 Ni c1 Fe d1 Mn e1 A f O g1 （Ⅱ）；
wherein b1 is more than or equal to 0.67 and less than or equal to 1.25,0.15, c1 is more than or equal to 0.35,0.15, d1 is more than or equal to 0.35,0.25, e1 is more than or equal to 0.66,0.15, f is more than or equal to 0.35, and c1+d1+e1+f= 1,1.75 is more than or equal to g1 and less than or equal to 2.25; a is a doping element selected from at least one of Cu, zn, ti, sc, V, co, zr, sb, al, mg, K, ga, li, mo, si, ce, sn; the algebraic sum of the positive and negative valencies of Na, ni, fe, mn, A, O in formula (II) is 0.
In the technical scheme, the doping element is used for providing larger interlayer spacing in the shell layer material so as to improve the stability of sodium ion deintercalation, thereby improving the performance of the positive electrode material. On the other hand, the addition of the doping element is beneficial to improving the cycle performance of the battery and reducing the capacity attenuation in the cycle process.
Further, in the shell material, the difference between the maximum value and the minimum value of the molar concentration of the doping element A is less than or equal to 35%; wherein the molar concentration of the doping element A is the proportion of the amount of the substance of the doping element A to the sum of the amounts of Ni, fe, mn and the substance of the doping element A.
In the technical scheme, the molar concentration gradient difference of the doping element A is less than 35%. In the shell material, the content of the doping element A is gradually increased from inside to outside; generally, there is little doping element at the interface between the shell material and the core material, and thus the molar concentration is typically 0. The molar concentration of the doping element a is greatest at the outermost side of the shell material, i.e. at the surface of the layered oxide. Wherein the molar concentration of the doping element A is the ratio of the amount of substances in the quaternary system; the quaternary system is four elements of Ni, fe, mn and doping element A.
The invention also provides a preparation method of the layered oxide, which comprises the following steps: s10: mixing a sodium source with the ternary precursor to perform sectional sintering to obtain a precursor oxide; s20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
In the preparation process of the layered oxide, the ternary precursor oxide can be obtained by sintering in the step S10, then doping elements are mixed, the second sintering is carried out, and the shell layer material is constructed according to the penetration of the doping elements from outside to inside of the precursor oxide and the doping depth of the precursor oxide. Wherein the content of the doping element gradually decreases from outside to inside; the change of the interlayer spacing of sodium ions in the shell material is realized.
Further, in step S10, the step of sintering includes a first-stage temperature-raising sintering and a second-stage temperature-raising sintering; the technological parameters of one-stage heating sintering are set as follows: the sintering temperature is 400-700 ℃, the heating rate is 3-8 ℃/min, and the sintering time is 5-10h; the technological parameters of the two-stage heating sintering are set as follows: the sintering temperature is 800-1150 ℃, the heating rate is 1-4 ℃/min, and the sintering time is 1-6h; cooling to 100 ℃ at 5 ℃/min, and cooling to room temperature at 5 ℃/min in an oxygen atmosphere. In the technical scheme, the construction of the layered oxide core layer material and the shell layer material is realized by controlling the reaction temperature, the reaction time and the heating rate. Specifically, an oxide precursor is obtained through sectional sintering technology and specific technological parameters, the temperature is low in a first stage of heating sintering, the mixture of a sodium source and a ternary precursor is thermally decomposed into an oxide, and the sintering time is controlled to be 5-10 hours, so that the raw materials are fully decomposed and combined to form a nickel-cobalt-manganese-sodium compound. Further, the second-stage heating sintering is carried out, the sintering temperature is heated to 800-1150 ℃ at the speed of 1-4 ℃/min, and the ion diffusion in the solid phase is promoted at a higher temperature. Preferably, the technological parameters of one-stage temperature-rising sintering are set as follows: the sintering temperature is 650 ℃, the heating rate is 5 ℃/min, and the sintering time is 8h. Preferably, the technological parameters of the two-stage temperature-rising sintering are set as follows: the sintering temperature is 1000 ℃, the heating rate is 2 ℃/min, and the sintering time is 4 hours.
Further, in step S20, the sintering process parameters are set as follows: the sintering temperature is 300-700 ℃, the heating rate is 1-5 ℃/min, the sintering time is 2-10h, the cooling rate is 10-60 ℃/min, and when the temperature is reduced to 100 ℃, the temperature is reduced to room temperature in the oxygen atmosphere at 5 ℃/min.
In the technical scheme, deep doping of the doping component is realized by controlling parameters of the sintering process; and the shell layer material is constructed by doping components. Specifically, the penetration depth of the doping element is controlled in a rapid cooling mode, and when the cooling rate is 10-60 ℃/min, the shell layer material with the content of the doping element gradually increasing from inside to outside and further with the sodium ion interlayer spacing gradually increasing from inside to outside can be constructed. When the cooling rate is too slow, the penetration depth of the doping element is too large, so that the thickness of the core layer material is too small; when the cooling rate is too fast, the penetration depth of the doping element is too small, thereby resulting in a smaller thickness of the shell material. Thus, to achieve the present invention the core material occupies 40-80%; the shell material occupies 20-60% of the characteristics, and the cooling speed is controlled to be 10-60 ℃/min; preferably 20 deg.c/min.
Further, the sodium source comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide; and/or the ternary precursor comprises three elements of nickel, iron and manganese.
In the technical scheme, the raw materials of the ternary precursor are selected in multiple different modes, wherein the nickel source, the iron source and the manganese source can be carbonate-based compounds or hydroxyl compounds of nickel, iron and manganese. The specific sources are not limited, and the precursor contains four elements of sodium, nickel, iron and manganese according to the mass ratio in the component design. The nickel source comprises at least one of nickel oxide, nickel protoxide, nickel nitrate and nickel acetate; the iron source comprises at least one of ferric oxide, ferrous oxide and ferric nitrate; the manganese source comprises at least one of manganese carbonate, manganese acetate, manganese sesquioxide and manganese tetraoxide.
Further, the doping component includes at least one element of Cu, zn, ti, sc, V, co, zr, sb, al, mg, K, ga, li, mo, si, ce, sn. Specifically, the Cu source is CuO; the Zn source is ZnO; ti source is TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Sc source Sc 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the V source is V 2 O 5 、VO 2 、V 2 O 3 One or more of VO; the Co source is cobalt acetate; zr source is ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Sb source is Sb 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Al source is Al 2 O 3 、Al(OH) 3 One or more of (a) and (b); the Mg source is MgO, mg (OH) 2 One or more of (a) and (b); k source is KOH, K 2 One or more of S; ca source is CaO, caCO 3 One or more of (a) and (b); the Li source is Li 2 O、LiOH、Li 2 CO 3 One or more of (a) and (b); mo source is Na 2 MoO 4 The Si source is SiO 2 The Ce source is CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Sn source is SnO, sn 2 O 3 One or more of (a) and (b).
The invention also provides a positive electrode plate of the sodium ion battery, which comprises the layered oxide provided by any one of the above. Therefore, the technical scheme has the beneficial effects and is not repeated herein.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of a layered oxide according to an embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the related art, the sodium-rich layered oxide has a multi-layer structure, the interlayer of the layered oxide can be used for containing sodium ions, and generally, the smaller sodium interlayer spacing ensures more active sodium content in a bulk phase, but also can limit the deintercalation of sodium ions, and particularly, the layered oxide with the variable sodium ion interlayer spacing can solve the problem that the stability of the deintercalation of sodium ions is ensured while ensuring the sufficient active sodium content due to the fact that the stacking is easy to be blocked in the long-term deintercalation process so as to influence the stability of the material.
The reason that the repulsive force between oxygen and oxygen is reduced due to the electron localization effect between transition metal layers is slowed down based on a high-entropy system, the sodium ion interlayer spacing of the ternary sodium-rich layered oxide is between 3.2 and 3.4A, and the sodium ion interlayer spacing of the quaternary sodium-rich layered oxide is between 3.25 and 3.5A. Therefore, the invention realizes the change of the interlayer spacing of sodium ions through the construction of doping elements.
Specifically, in the present invention, the layered oxide includes a core layer material and a shell layer material, and in the thickness direction of the layered oxide, the core layer material occupies 2/5~4/5, and the shell layer material occupies 1/5~3/5; and the shell layer material is wrapped outside the core layer material. Wherein the core layer material is ternary sodium-rich layered oxide, namely oxide containing three elements, and sodium ions can be contained between layers of the oxide; the shell material is quaternary sodium-rich layered oxide, and further comprises doping elements on the basis of ternary.
In the preparation process, firstly, raw material proportioning is carried out according to component design, a ternary precursor oxide is obtained through sintering, and secondly, doping elements are mixed for secondary sintering; during sintering, the doping element gradually penetrates from the outside of the ternary precursor oxide inwards, and the doping concentration of the doping element also gradually decreases from outside to inside. The layered oxide can be divided into a core layer material and a shell layer material according to the doping condition of the doping element; the shell layer material is obtained by constructing the doping depth of the doping element, and the core layer material is obtained without the doping element.
The concentration of doping elements in the shell material is changed, so that the change of the sodium ion layer spacing is realized; specifically, the higher the concentration of the doping element, the larger the sodium ion interlayer spacing thereof; and further, the characteristic of the sodium ion interlayer spacing change of the layered oxide provided by the invention can be realized. Furthermore, by controlling the sintering temperature, the penetration depth of the doped component is constructed, the penetration depth of the doped element is controlled in a rapid cooling mode, and when the cooling rate is 10-60 ℃/min, the shell layer material with the content of the doped element gradually increasing from inside to outside and the interlayer spacing of sodium ions gradually increasing from inside to outside can be constructed.
Compared with the traditional ternary or quaternary sodium-rich layered oxide, the layered oxide provided by the invention has the characteristics of low entropy and high capacity of the ternary sodium-rich layered oxide and the characteristics of high stability of the quaternary sodium-rich layered oxide.
Furthermore, the sodium button half cell assembled by the layered oxide provided by the invention can provide 160-210 mAh/g discharge capacity under the condition of 0.1C multiplying power charge and discharge under the voltage window of 2-4.2V, and the capacity retention rate of 300 circles of the button half cell assembled by the layered oxide under the multiplying power of 10C with high cycle stability is 95-100%.
Example 1
The embodiment provides a method for preparing a layered oxide, which comprises the following steps:
s10: and (3) performing sectional sintering on the precursor containing the sodium source, the nickel source, the iron source and the manganese source to obtain the precursor oxide.
The precursor is a mixture of sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide; wherein, the molar ratio of each element satisfies Na: ni: fe: mn=1: 0.33:0.33:0.33.
the sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, and heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours; cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere. S20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
Wherein, the doping component selects copper oxide, and the mole ratio of each element satisfies Na: ni: fe: mn: cu=1: 0.33:0.33:0.33:0.05.
the sintering process parameters are set as follows: heating to 500 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, cooling to 100 ℃ at a cooling rate of 20 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
The present example also provides a layered oxide prepared by the above-described preparation method. Fig. 1 is an SEM image thereof, and by EDS scanning the cross section of the layered oxide provided in this embodiment, the sizes of the core layer material and the shell layer material can be effectively quantified, and the molar content of the doping element in the shell layer material can be obtained.
The layered oxide provided by the embodiment comprises a core layer material and a shell layer material wrapping the core layer material; wherein the molecular formula of the core layer material is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the shell layer material is NaNi 0.3 Fe 0.3 Mn 0.3 Cu 0.1 O 2 。
The thickness of the core layer material and the shell layer material of the layered oxide provided in this example were tested. The core layer material is adhered to the shell layer material, and the shell layer material is divided into an inner area, a middle area and an outer area; the sodium ion layer spacing of the three different regions was measured and the sodium layer change rate K was calculated d The results are shown in Table 1.
Comparative example 1
This comparative example was used for the comparison of example 1 to prepare NaNi 0.33 Fe 0.33 Mn 0.33 O 2 Materials: sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide are mixed according to Na: ni: fe: mn=1: 0.33:0.33: mixing the elements in a molar ratio of 0.33 uniformly, and sintering to obtain the material. Wherein, sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours, cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
NaNi provided in comparative example 0.33 Fe 0.33 Mn 0.33 O 2 The materials were tested, including measurement of the sodium ion layer spacing in the materials, and the results are shown in table 1.
Example 2
The embodiment provides a method for preparing a layered oxide, which comprises the following steps:
s10: and (3) performing sectional sintering on the precursor containing the sodium source, the nickel source, the iron source and the manganese source to obtain the precursor oxide.
The precursor is a mixture of sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide; wherein, the molar ratio of each element satisfies Na: ni: fe: mn=1: 0.33:0.33:0.33.
the sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours, cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
S20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
Wherein, the doping component selects copper oxide, and the mole ratio of each element satisfies Na: ni: fe: mn: cu=1: 0.33:0.33:0.33:0.05.
the sintering process parameters are set as follows: heating to 500 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, cooling to 100 ℃ at a cooling rate of 20 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
The present example also provides a layered oxide prepared by the above-described preparation method.
The layered oxide provided by the embodiment comprises a core layer material and a shell layer material wrapping the core layer material; wherein the molecular formula of the core layer material is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the shell layer material is NaNi 0.3 Fe 0.3 Mn 0.3 Cu 0.1 O 2 。
The thickness of the core layer material and the shell layer material of the layered oxide provided in this example were tested. The core layer material is adhered to the shell layer material, and the shell layer material is divided into an inner area, a middle area and an outer area; the sodium ion layer spacing of the three different regions was measured and the sodium layer change rate K was calculated d The results are shown in Table 1.
Example 3
The embodiment provides a method for preparing a layered oxide, which comprises the following steps:
s10: and (3) performing sectional sintering on the precursor containing the sodium source, the nickel source, the iron source and the manganese source to obtain the precursor oxide.
The precursor is a mixture of sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide; wherein, the molar ratio of each element satisfies Na: ni: fe: mn=1: 0.33:0.33:0.33.
the sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours, cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
S20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
Wherein, the doping component selects copper oxide, and the mole ratio of each element satisfies Na: ni: fe: mn: cu=1: 0.33:0.33:0.33:0.1.
the sintering process parameters are set as follows: heating to 500 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, cooling to 100 ℃ at a cooling rate of 20 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
The present example also provides a layered oxide prepared by the above-described preparation method.
The layered oxide provided by the embodiment comprises a core layer material and a shell layer material wrapping the core layer material; wherein the molecular formula of the core layer material is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the shell layer material is NaNi 0.28 Fe 0.28 Mn 0.28 Cu 0.16 O 2 。
The thickness of the core layer material and the shell layer material of the layered oxide provided in this example were tested. The core layer material is adhered to the shell layer material, and the shell layer material is divided into an inner area, a middle area and an outer area; the sodium ion layer spacing of the three different regions was measured and the sodium layer change rate K was calculated d The results are shown in Table 1.
Example 4
The embodiment provides a method for preparing a layered oxide, which comprises the following steps:
s10: and (3) performing sectional sintering on the precursor containing the sodium source, the nickel source, the iron source and the manganese source to obtain the precursor oxide.
The precursor is a mixture of sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide; wherein, the molar ratio of each element satisfies Na: ni: fe: mn=1: 0.33:0.33:0.33.
the sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours, cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
S20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
Wherein, zinc oxide is selected as the doping component, and the molar ratio of each element satisfies Na: ni: fe: mn: zn=1: 0.33:0.33:0.33:0.05.
the sintering process parameters are set as follows: heating to 500 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, cooling to 100 ℃ at a cooling rate of 20 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
The present example also provides a layered oxide prepared by the above-described preparation method.
The layered oxide provided by the embodiment comprises a core layer material and a shell layer material wrapping the core layer material; wherein the molecular formula of the core layer material is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the shell layer material is NaNi 0.3 Fe 0.3 Mn 0.3 Zn 0.1 O 2 。
The thickness of the core layer material and the shell layer material of the layered oxide provided in this example were tested. The core layer material is adhered to the shell layer material, and the shell layer material is divided into an inner area, a middle area and an outer area; the sodium ion layer spacing of the three different regions was measured and the sodium layer change rate K was calculated d The results are shown in Table 1.
Example 5
The embodiment provides a method for preparing a layered oxide, which comprises the following steps:
s10: and (3) performing sectional sintering on the precursor containing the sodium source, the nickel source, the iron source and the manganese source to obtain the precursor oxide.
The precursor is a mixture of sodium carbonate, nickel oxide, ferroferric oxide and manganic oxide; wherein, the molar ratio of each element satisfies Na: ni: fe: mn=1: 0.33:0.33:0.33.
the sintering process parameters are set as follows: heating to 650 ℃ at a heating rate of 5 ℃/min, sintering for 8 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, sintering for 4 hours, cooling to 100 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
S20: mixing the precursor oxide with the doping component, and sintering to obtain the layered oxide.
Wherein, zinc oxide is selected as the doping component, and the molar ratio of each element satisfies Na: ni: fe: mn: zn=1: 0.33:0.33:0.33:0.05.
the sintering process parameters are set as follows: heating to 500 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, cooling to 100 ℃ at a cooling rate of 20 ℃/min, and cooling to room temperature at a cooling rate of 5 ℃/min in an oxygen atmosphere.
The present example also provides a layered oxide prepared by the above-described preparation method.
The layered oxide provided by the embodiment comprises a core layer material and a shell layer material wrapping the core layer material; wherein the molecular formula of the core layer material is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the shell layer material is NaNi 0.3 Fe 0.3 Mn 0.3 Zn 0.1 O 2 。
The thickness of the core layer material and the shell layer material of the layered oxide provided in this example were tested. The core layer material is adhered to the shell layer material, and the shell layer material is divided into an inner area, a middle area and an outer area; the sodium ion layer spacing of the three different regions was measured and the sodium layer change rate K was calculated d The results are shown in Table 1.
TABLE 1 structural Properties of materials
The molar ratios of the elements in the materials provided in examples 1-5 and comparative example 1 were tested. The test results are shown in Table 2.
Table 2 molar proportions of transition metal elements of the materials
The electrical properties of the cells prepared from the materials provided in examples 1-5 and comparative example 1 were tested. The specific operation is as follows:
mixing positive electrode powder, a conductive agent Super-P and a binder PVDF according to a mass ratio of 92:4:4, adding an appropriate amount of NMP solution to form slurry, and carrying out the steps ofCoating on aluminum foil, drying, and baking at 120deg.C in vacuum oven for 12 hr. Then, the battery was assembled in a dry room, using aluminum foil coated with hard carbon as a negative electrode, and using 1mol/L NaPF 6 And (3) mixing organic solvents with a volume ratio EC and EMC=3:7 as electrolyte to assemble the soft package battery. And (3) using a constant current charge-discharge mode, performing a first-cycle charge-discharge test at a voltage window of 1.5-4.3V under 40mA current, and then performing a 600-week cycle test at 400 mAh. The results of the electrical properties are shown in Table 3.
Wherein the positive electrode powders were prepared from the materials provided in examples 1 to 5 and comparative examples, respectively.
TABLE 3 electrochemical Properties of materials
Example 6
The present example provides a layered oxide and a method for preparing the same, wherein the method for preparing the same is described in example 1, differing in various process parameters and raw material selections; see table 4 for specific process parameters.
TABLE 4 Table 4
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (6)

1. A layered oxide, wherein the layered oxide comprises a core material and a shell material coating at least part of the surface of the core material;
wherein the core layer material is ternary sodium-rich layered oxide, and the shell layer material is quaternary sodium-rich layered oxide; the ternary sodium-rich layered oxide is an oxide composed of nickel, iron, manganese and sodium, and the quaternary sodium-rich layered oxide is an oxide composed of nickel, iron, manganese, doping elements and sodium;
wherein the doping element is selected from at least one of Cu, zn, sc, sb, mg, K, sn;
the composition of the core layer material is shown as a formula (I):
Na b Ni c Fe d Mn e O g (Ⅰ)；
wherein b is more than or equal to 0.67 and less than or equal to 1.25,0.15, c is more than or equal to 0.35,0.15, d is more than or equal to 0.35,0.25 and less than or equal to e is more than or equal to 0.66, and c+d+e= 1,1.75 and g is more than or equal to 2.25;
the algebraic sum of the positive and negative valence of Na, ni, fe, mn, O in the formula (I) is 0;
the composition of the shell material is shown as a formula (II):
Na b1 Ni c1 Fe d1 Mn e1 A f O g1 （Ⅱ）；
wherein b1 is more than or equal to 0.67 and less than or equal to 1.25,0.15, c1 is more than or equal to 0.35,0.15, d1 is more than or equal to 0.35,0.25, e1 is more than or equal to 0.66,0.15, f is more than or equal to 0.35, and c1+d1+e1+f= 1,1.75 is more than or equal to g1 and less than or equal to 2.25;
a is a doping element selected from at least one of Cu, zn, sc, sb, mg, K, sn;
the algebraic sum of the positive and negative valence of Na, ni, fe, mn, A, O in the formula (II) is 0;
thickness D of the core material 1 Thickness D with the layered oxide 0 Satisfy D of 0.4-0 1 /D 0 ≤0.8；
Average value L of sodium ion interlayer spacing in shell material 1 Average value L of interlayer spacing with sodium ions in the core layer material 2 The following relationship is satisfied: 0 a < L 1 -L 2 ≤0.2Å；
The sodium ion interlayer spacing in the shell layer material gradually increases along the direction from the core layer material to the shell layer material;
in the shell material, the difference between the maximum value and the minimum value of the molar concentration of the doping element is less than or equal to 35%; wherein the molar concentration of the doping element is the ratio of the amount of the substance of the doping element to the sum of the amounts of Ni, fe, mn and the substance of the doping element;
the layered oxide is prepared by the following method:
s10: mixing a sodium source with the ternary precursor to perform sectional sintering to obtain a precursor oxide;
s20: mixing the precursor oxide with a doping component, and sintering to obtain the layered oxide;
in step S20, the sintering process parameters are set as follows: the sintering temperature is 300-700 ℃, the heating rate is 1-5 ℃/min, the sintering time is 2-10h, the cooling rate is 10-60 ℃/min, and when the temperature is reduced to 100 ℃, the temperature is reduced to room temperature in the oxygen atmosphere at 5 ℃/min.
2. The layered oxide according to claim 1, wherein,
sodium layer change rate K of the layered oxide d The numerical ranges of (2) are as follows: k is more than 0 d ≤10 -3 ；
Wherein K is d The calculation mode of (2) is as follows: k (K) d = ( L 1 - L 2 )/D 2 ；
L 1 An average value of the interlayer spacing of sodium ions in the shell material;
L 2 is the average value of the sodium ion interlayer spacing in the core layer material;
D 2 is the thickness of the shell material.
3. A method for producing a layered oxide, characterized by being used for producing the layered oxide as claimed in claim 1 or 2, comprising the steps of:
s10: mixing a sodium source with the ternary precursor to perform sectional sintering to obtain a precursor oxide;
s20: and mixing the precursor oxide with a doping component, and sintering to obtain the layered oxide.
4. A process according to claim 3, wherein,
in step S10, the step of sintering includes one-stage temperature-raising sintering and two-stage temperature-raising sintering;
the technological parameters of the one-stage temperature-rising sintering are set as follows: the sintering temperature is 400-700 ℃, the heating rate is 3-8 ℃/min, and the sintering time is 5-10h;
the technological parameters of the two-stage heating sintering are set as follows: the sintering temperature is 800-1150 ℃, the heating rate is 1-4 ℃/min, and the sintering time is 1-6h; cooling to 100 ℃ at 5 ℃/min, and cooling to room temperature at 5 ℃/min in an oxygen atmosphere.
5. A process according to claim 3, wherein,
the sodium source comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide.
6. A positive electrode sheet for a sodium ion battery, comprising the layered oxide as claimed in claim 1 or 2.
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