CN108258239B - Sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a sodium ion battery anode material and a preparation method and application thereof. The positive electrode material provided by the invention comprises doped Prussian blue, wherein the Prussian blue contains sodium elements, and the positive electrode material does not contain water. The preparation method of the cathode material provided by the invention comprises the following steps: (1) mixing a solution A and a solution B to obtain a suspension, wherein the solution A is a mixed solution of sodium ferrocyanide and sodium chloride, and the solution B is a mixed solution of a doping source and a complexing agent; (2) and (2) carrying out solid-liquid separation on the suspension obtained in the step (1), taking the solid and drying to obtain the cathode material. The positive electrode material of the sodium ion battery provided by the invention has a single-voltage platform and excellent charging and discharging performance, and is particularly suitable for being used as a positive electrode of a solid sodium ion battery because the positive electrode material does not contain water. The preparation method of the anode material provided by the invention is simple in process, low in cost and suitable for industrial application.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to a sodium ion battery positive electrode material, and a preparation method and application thereof.
Background
In recent years, with the gradual development and application of lithium ion batteries from portable electronic equipment to high-power electric vehicles, large-scale energy storage power stations, smart power grids and the like, the demand of the lithium ion batteries is increasing day by day, but the sustainable development of the lithium ion batteries is limited by limited lithium resources. And the sodium reserves are abundant, and the sodium ion battery is an important supplement of the lithium ion battery in large-scale energy storage application. Sodium and lithium are in the same main group and are similar in chemical properties, so that it is feasible to construct a sodium ion battery similar to the working principle of a lithium ion battery.
However, the safety problem during charge and discharge is the most prominent problem in both lithium ion batteries and sodium ion batteries. One of the most effective approaches to solving this safety problem is to develop solid-state ion batteries. And the positive electrode material tends to have a decisive influence on the cost and performance of the ion secondary battery. The development of a novel high-performance and low-cost cathode material is also a hot spot of the academic world for the development of solid-state secondary batteries. The Prussian blue material can be used for reversibly extracting and inserting sodium ions, and the Prussian blue material and a liquid electrolyte form a battery system, so that a theoretical capacity of the Prussian blue material is as high as 170mAh/g, and a sodium storage potential platform is higher (a high platform is 3.34V, and a low platform is 2.96V), so that the Prussian blue material is considered to be one of the extremely promising positive electrode materials. However, the prussian blue and the derivatives thereof are numerous, and common prussian blue includes iron manganese based prussian blue, iron nickel based prussian blue, iron copper based prussian blue, iron cobalt based prussian blue, iron based prussian blue, iron zinc based prussian blue and the like. The prussian blue has different specific capacities in liquid sodium-ion batteries and also has greatly different cycle performances. In addition, the prussian blue positive electrode materials reported at present cannot contain water completely, and the electrode materials containing water are difficult to be used in solid-state batteries.
CN106920964A discloses a Prussian blue type sodium ion battery anode material substituted by transition metal elements in a gradient manner and a preparation method thereof. The material is prepared by substituting transition metal elements for iron ions in iron-nitrogen octahedron in Prussian blue crystal lattice from the interior of crystal grain to the surface according to concentration gradient, and the molecular formula of the transition metal elements is NaxMyFe1-y[Fe(CN)6]z·nH2O and M are substituted elements. The Prussian blue sodium ion battery anode material provided by the scheme contains crystal water and is difficult to be in solid sodium ionsThe method is applied to batteries.
Therefore, the development of a prussian blue-based positive electrode material capable of being applied to a solid-state sodium ion battery is of great significance in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a positive electrode material of a sodium-ion battery, and a preparation method and application thereof. The sodium ion battery anode material provided by the invention contains no water, has excellent electrochemical performance and low preparation cost, and can be applied to solid sodium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a cathode material, which comprises doped prussian blue, wherein the prussian blue contains sodium elements, and the cathode material contains no water.
The doped Prussian blue sodium ion battery anode material provided by the invention has few structural defects and complete crystallization, so that the doped Prussian blue sodium ion battery anode material can be free of water in any form, namely free water and crystallization water are not contained. The characteristics enable the anode material provided by the invention to meet the requirements of solid sodium-ion batteries.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the substance doped in the positive electrode material is a divalent transition metal element.
Preferably, the divalent transition metal element includes any one or a combination of at least two of manganese, cobalt, nickel, copper, zinc, or iron, typically but not limited to a combination of: a combination of manganese and cobalt, a combination of nickel and copper, a combination of zinc and iron, and the like.
As a preferable technical scheme of the invention, the molecular formula of the cathode material is NaxMyFez(CN)6Wherein M is a divalent transition metal element, 1. ltoreq. x.ltoreq.2, such as 1, 1.2, 1.4, 1.6, 1.8 or 2, etc., but not limited to the recited values, and other unrecited values within the numerical range are equally applicable; 0.5. ltoreq. y.ltoreq.1, for example 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable; x +2(y + z) ≦ 6, for example, x +2(y + z) is 4, 4.5, 5, 5.5, or 6, and when x +2(y + z) ≦ 6, there is almost no defect, and as the deviation of the distance 6 becomes larger, there is a defect generation. In the invention, z is more than or equal to 0.
In a second aspect, the present invention provides a method for producing the positive electrode material according to the first aspect, the method comprising the steps of:
(1) mixing a solution A and a solution B to obtain a suspension, wherein the solution A is a mixed solution of sodium ferrocyanide and sodium chloride, and the solution B is a mixed solution of a doping source and a complexing agent;
(2) and (2) carrying out solid-liquid separation on the suspension obtained in the step (1), taking the solid and drying to obtain the cathode material.
In the invention, the addition of the sodium chloride and the complexing agent plays an important role in finally obtaining the non-aqueous sodium ion battery anode material, the sodium chloride and the complexing agent play a slow release role in the forming process of the Prussian blue, and the crystallization speed of the suspension in the mixing operation is slowed down, so that the finally obtained anode material has few defects and high crystallinity, and the drying and dehydration of the anode material obtained by the preparation method can be realized just because of the characteristics, and the anode material capable of meeting the requirements of the solid-state battery can be obtained.
As a preferred embodiment of the present invention, the suspension in step (1) has a sodium chloride concentration of 1 wt% to 10 wt%, for example 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt% or 10 wt%, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable. In the invention, the final concentration of sodium chloride in the reaction system has a great influence on the generated Prussian blue electrode cathode material, if the mass concentration of sodium chloride in the suspension is lower than 1 wt%, the sodium content of the generated Prussian blue is lower, and if the mass concentration of sodium chloride in the suspension is higher than 10 wt%, the formed Prussian blue has a heterogeneous phase.
Preferably, the concentration of sodium ferrocyanide in the solution A in the step (1) is 0.02mol/L to 0.2mol/L, such as 0.02mol/L, 0.06mol/L, 0.08mol/L, 0.1mol/L, 0.15mol/L or 0.2mol/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sodium ferrocyanide of step (1) is sodium ferrocyanide decahydrate.
Preferably, the solvent of the solution A in the step (1) is water, preferably deionized water.
Preferably, the doping source in step (1) is a divalent transition metal salt.
Preferably, the divalent transition metal salt comprises a divalent transition metal chloride and/or a divalent transition metal sulfate. In the present invention, the divalent transition metal chloride and/or divalent transition metal sulfate means: the metal sulfate may be a divalent transition metal chloride, a divalent transition metal sulfate, or a combination of a divalent transition metal chloride and a divalent transition metal sulfate.
Preferably, the divalent transition metal salt includes any one or a combination of at least two of manganese, cobalt, nickel, copper, zinc or ferrous salts, typically but not limited to the following combinations: combinations of manganese and cobalt salts, nickel and copper salts, zinc and ferrous salts, and the like.
Preferably, the concentration of the doping source in the solution B in the step (1) is 0.02mol/L to 0.2mol/L, such as 0.02mol/L, 0.06mol/L, 0.08mol/L, 0.1mol/L, 0.15mol/L or 0.2mol/L, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the complexing agent in step (1) comprises any one or a combination of at least two of sodium citrate, ethylenediaminetetraacetic acid (EDTA), acetic acid, or sulfosalicylic acid, typically but not limited to, a combination of: combinations of sodium citrate and ethylenediaminetetraacetic acid (EDTA), combinations of ethylenediaminetetraacetic acid (EDTA) and acetic acid, combinations of acetic acid and sulfosalicylic acid, and the like.
Preferably, the molar ratio of the complexing agent to the doping source in step (1) is 1:1 to 2:1, such as 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2:1, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, in the solution B in step (1), the solvent is water, preferably deionized water.
In the preferred embodiment of the present invention, in the step (1), the molar ratio of the sodium ferrocyanide to the doping source in the system formed by mixing the solution a and the solution B is 1 to 3, for example, 1, 1.5, 2, 2.5 or 3, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the temperature of the mixing operation in step (1) is 25 ℃ to 70 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing operation of step (1) is carried out under stirring conditions.
Preferably, the stirring rate is from 300rpm to 1000rpm, such as 300rpm, 500rpm, 700rpm, 900rpm or 1000rpm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the mixing operation of step (1) is dropwise adding the solution A and the solution B into the aqueous solution. According to the invention, the dropwise adding mode is adopted, so that the materials can be uniformly mixed, and the crystallization speed is controlled to prevent the materials from being too fast.
Preferably, the aqueous solution is water.
Preferably, the dropping rate of the solution A and the dropping rate of the solution B are independently 0.1mL/min to 1mL/min, such as 0.1mL/min, 0.2mL/min, 0.4mL/min, 0.6mL/min, 0.8mL/min, or 1mL/min, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the dropping rate of the solution A and the dropping rate of the solution B are the same.
As a preferable embodiment of the present invention, the step (1) further comprises: and carrying out hydrothermal reaction on the suspension. According to the invention, the hydrothermal reaction method is adopted to treat the suspension, so that the crystallinity of the obtained cathode material can be further improved, the structural defects are fewer, and the performance is better.
Preferably, the hydrothermal reaction is carried out at a temperature of 150 ℃ to 200 ℃, for example 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable.
Preferably, the hydrothermal reaction time is 15h to 24h, such as 15h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the hydrothermal reaction is carried out in a hydrothermal kettle.
In a preferred embodiment of the present invention, in the step (2), the solid-liquid separation is centrifugal separation or suction filtration separation.
Preferably, step (2) further comprises: solid-liquid separation was performed by washing with water before drying to obtain a solid.
Preferably, in step (2), the drying is performed in a vacuum drying oven.
Preferably, in step (2), the drying temperature is 100 ℃ to 120 ℃, for example 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in step (2), the drying time is 24h to 48h, such as 24h, 28h, 32h, 36h, 40h, 44h or 48h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in step (2), the degree of vacuum for drying is 10mTorr-15mTorr, such as 10mTorr, 11mTorr, 12mTorr, 13mTorr, 14mTorr, or 15mTorr, but not limited to the recited values, and other values not recited in this range of values are equally applicable.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) under the stirring conditions of 25-70 ℃ and 300-1000 rpm, dropwise adding the solution A and the solution B into water at a dropwise adding speed of 0.1-1.0 mL/min, wherein the dropwise adding speed of the solution A is the same as that of the solution B, and after the solution A and the solution B are completely dropwise added, placing the obtained suspension into a hydrothermal kettle for hydrothermal reaction at 150-200 ℃ for 15-24 h to obtain a suspension after the hydrothermal reaction; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, the solution B is a mixed solution formed by dissolving a doping source and a complexing agent into water, and the doping source is divalent transition metal chloride and/or divalent transition metal sulfate;
(2) carrying out centrifugal separation or suction filtration separation on the suspension obtained after the hydrothermal reaction in the step (1), taking a solid, and drying the obtained solid in a vacuum drying oven at 100-120 ℃ and under the vacuum degree of 10mTorr-15mTorr for 24-48 h to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 1 wt% -10 wt%; in the solution A, the concentration of the sodium ferrocyanide is 0.02-0.2 mol/L; in the solution B, the concentration of divalent transition metal ions is 0.02mol/L-0.2mol/L, and the molar ratio of the complexing agent to the divalent transition metal ions is 1:1-2: 1; in the system formed by mixing the solution A and the solution B, the molar ratio of the sodium ferrocyanide to the divalent transition metal ions is 1-3.
In a third aspect, the present invention provides a use of the positive electrode material according to the first aspect for a positive electrode of a solid-state sodium-ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sodium ion battery anode material provided by the invention has high crystallinity, few defects, single voltage platform and excellent charging and discharging performance, and is particularly suitable for being used as an anode of a solid sodium ion battery because the material does not contain water.
(2) The preparation method of the cathode material provided by the invention has the advantages of simple process and low cost, is suitable for industrial application, can be popularized and applied to the preparation of other Prussian blue cathode materials, and the synthesized material can also be popularized and applied to other solid-state secondary batteries.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of a positive electrode material obtained after centrifugal separation in step (2) of example 2 of the present invention before drying;
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a dried cathode material finally prepared in example 2 of the present invention;
fig. 3 is a first-cycle charge-discharge curve of a positive electrode material obtained after centrifugal separation before drying to manufacture a battery in step (2) of example 2 of the present invention;
fig. 4 is a first cycle charge and discharge curve of a battery fabricated from the dried positive electrode material finally prepared in example 2 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a preparation method of a cathode material, which comprises the following specific steps:
(1) under the stirring conditions of 25 ℃ and 500rpm, dropwise adding the solution A and the solution B into water at a dropwise adding speed of 0.5mL/min until the dropwise adding is complete to obtain a suspension; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, and the solution B is a mixed solution formed by dissolving cobalt chloride and complexing agent sodium citrate into water;
(2) centrifuging the suspension liquid obtained in the step (1), taking a solid, and drying the solid in a vacuum drying oven at 100 ℃ and a vacuum degree of 10mTorr for 48 hours to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 1 wt%, and in the solution A, the concentration of sodium ferrocyanide is 0.02 mol/L; in solution B, Co2+The concentration of (A) is 0.02mol/L, and complexing agents of sodium citrate and Co2+In a molar ratio of 1.5: 1; in the system formed by mixing the solution A and the solution B, sodium ferrocyanide and Co2+Is 2.
The molecular formula of the solid-state sodium-ion battery cathode material obtained in the embodiment is Na1.68Co0.95Fe1.0(CN)6High crystallinity, less defects and no water.
The positive electrode material obtained by the embodiment has a single voltage platform and excellent charge and discharge performance.
The cathode material obtained in the embodiment can be mixed with an amorphous carbon material and Na0.66[Li0.22Ti0.78]O2、Na0.6[Cr0.6Ti0.4]O2、Na2Ti3O7And cathode materials such as Sn/C composite materials and the like form the solid-state sodium ion battery.
Example 2
The embodiment provides a preparation method of a cathode material, which comprises the following specific steps:
(1) under the stirring conditions of 50 ℃ and the speed rate of 300rpm, dropwise adding the solution A and the solution B into water at the dropwise adding speed of 0.1mL/min, and placing the obtained suspension into a hydrothermal kettle for hydrothermal reaction at 175 ℃ for 20 hours to obtain the suspension after the hydrothermal reaction; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, and the solution B is a mixed solution formed by dissolving manganese chloride and complexing agent EDTA into water;
(2) centrifuging the suspension obtained after the hydrothermal reaction in the step (1), taking a solid, and drying the obtained solid in a vacuum drying oven at 110 ℃ and a vacuum degree of 12.5mTorr for 36 hours to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 5 wt%, and in the solution A, the concentration of sodium ferrocyanide is 0.1 mol/L; in solution B, Mn2+Is 0.1mol/L, complexing agents EDTA and Mn2+In a molar ratio of 1: 1; in the system formed by mixing the solution A and the solution B, sodium ferrocyanide and Mn2+Is 1.
The molecular formula of the solid-state sodium-ion battery cathode material obtained in the embodiment is Na2MnFe(CN)6High crystallinity, less defects and no water.
The positive electrode material obtained by the embodiment has a single voltage platform and excellent charge and discharge performance.
The cathode material obtained in the embodiment can be mixed with an amorphous carbon material and Na0.66[Li0.22Ti0.78]O2、Na0.6[Cr0.6Ti0.4]O2、Na2Ti3O7And cathode materials such as Sn/C composite materials and the like form the solid-state sodium ion battery.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the positive electrode material obtained after the centrifugal separation in step (2) of this example before drying, and it can be seen from the image that the obtained prussian blue crystal particles exhibit monodispersity and have a typical hexagonal morphology in some cases.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the dried cathode material finally prepared in this example, from which it can be seen that there is no significant change in morphology before and after drying.
Fig. 3 is the first cycle charge and discharge curve of the positive electrode material obtained after centrifugal separation in step (2) of this example after the battery was fabricated before drying, from which it can be seen that the charge and discharge polarization was relatively large and the first cycle discharge capacity was only 92 mAh/g.
Fig. 4 is a first-cycle charge-discharge curve of the dried cathode material finally prepared in this example after being made into a battery, and it can be seen from the curve that charge-discharge polarization is significantly reduced and the first-cycle discharge capacity is increased to 150 mAh/g.
Example 3
The embodiment provides a preparation method of a cathode material, which comprises the following specific steps:
(1) under the stirring conditions of 70 ℃ and the speed of 1000rpm, dropwise adding the solution A and the solution B into water at the dropwise adding speed of 1.0mL/min, and after complete dropwise adding, placing the obtained suspension into a hydrothermal kettle for hydrothermal reaction at 200 ℃ for 15 hours to obtain a suspension after the hydrothermal reaction; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, and the solution B is a mixed solution formed by dissolving nickel sulfate and complexing agent acetic acid into water;
(2) centrifuging the suspension obtained after the hydrothermal reaction in the step (1), taking a solid, and drying the obtained solid in a vacuum drying oven at 120 ℃ and a vacuum degree of 15mTorr for 24 hours to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 10 wt%, and in the solution A, the concentration of sodium ferrocyanide is 0.2 mol/L; in solution B, Ni2+The concentration of (A) is 0.2 mol/L; in a system formed by mixing the solution A and the solution B, complexing agent acetic acid and Ni2+In a molar ratio of 2: 1; in the system formed by mixing solution A and solution B, sodium ferrocyanide and Ni2+Is 3.
The molecular formula of the solid-state sodium-ion battery cathode material obtained in the embodiment is Na1.55Ni0.78Fe0.84(CN)6High crystallinity, less defects and no water.
The positive electrode material obtained by the embodiment has a single voltage platform and excellent charge and discharge performance. .
The cathode material obtained in the embodiment can be mixed with an amorphous carbon material and Na0.66[Li0.22Ti0.78]O2、Na0.6[Cr0.6Ti0.4]O2、Na2Ti3O7And cathode materials such as Sn/C composite materials and the like form the solid-state sodium ion battery.
Example 4
The embodiment provides a preparation method of a cathode material, which comprises the following specific steps:
(1) under the stirring conditions of 45 ℃ and 800rpm, dropwise adding the solution A and the solution B into water at a dropwise adding speed of 0.7mL/min, and after complete dropwise adding, placing the obtained suspension into a hydrothermal kettle for hydrothermal reaction at 150 ℃ for 24 hours to obtain a suspension after the hydrothermal reaction; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, and the solution B is a mixed solution formed by dissolving zinc chloride and a complexing agent sulfosalicylic acid into water;
(2) centrifuging the suspension obtained after the hydrothermal reaction in the step (1), taking a solid, and drying the obtained solid in a vacuum drying oven at 115 ℃ and a vacuum degree of 13mTorr for 30 hours to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 7 wt%, and in the solution A, the concentration of sodium ferrocyanide is 0.08 mol/L; in solution B, Zn2+Has a concentration of 0.12mol/L, and complexing agents of sulfosalicylic acid and Zn2+In a molar ratio of 1.5: 1; in the system formed by mixing the solution A and the solution B, sodium ferrocyanide and Zn2+Is 1.5.
The molecular formula of the solid-state sodium-ion battery cathode material obtained in the embodiment is Na1.69Zn0.91Fe0.83(CN)6High crystallinity, less defects and no water.
The positive electrode material obtained by the embodiment has a single voltage platform and excellent charge and discharge performance. .
The cathode material obtained in the embodiment can be mixed with an amorphous carbon material and Na0.66[Li0.22Ti0.78]O2、Na0.6[Cr0.6Ti0.4]O2、Na2Ti3O7And cathode materials such as Sn/C composite materials and the like form the solid-state sodium ion battery.
Comparative example 1
The procedure of this comparative example was as in example 2 except that in step (1), sodium chloride was not used.
The result is that the cathode material obtained by the comparative example has low sodium content, poor crystallinity and a plurality of defects, can not be completely dehydrated by drying, has poor electrochemical performance, and can not be used as a cathode material of a solid sodium-ion battery.
The embodiment and the comparative example show that the cathode material provided by the invention has few defects, high crystallinity, no water and good electrochemical performance, and can be used for a solid sodium-ion battery. The comparative example did not adopt the scheme provided by the present invention, and thus the effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (37)
1. The positive electrode material is characterized by comprising doped Prussian blue, wherein the Prussian blue contains sodium elements, and the positive electrode material does not contain water;
the positive electrode material is prepared by adopting the following method, and the preparation method comprises the following steps:
(1) mixing a solution A and a solution B to obtain a suspension, wherein the solution A is a mixed solution of sodium ferrocyanide and sodium chloride, the solution B is a mixed solution of a doping source and a complexing agent, and the molar ratio of the sodium ferrocyanide to the doping source is 1-3;
(2) and (2) carrying out solid-liquid separation on the suspension obtained in the step (1), taking the solid and drying to obtain the cathode material.
2. The positive electrode material according to claim 1, wherein the substance doped in the positive electrode material is a divalent transition metal element.
3. The positive electrode material according to claim 2, wherein the divalent transition metal element includes any one of a manganese element, a cobalt element, a nickel element, a copper element, a zinc element, or an iron element, or a combination of at least two thereof.
4. According to any of claims 1-3The cathode material is characterized in that the molecular formula of the cathode material is NaxMyFez(CN)6Wherein M is a divalent transition metal element, x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0.5 and less than or equal to 1, and x +2(y + z) is less than or equal to 6.
5. The method for producing a positive electrode material according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) mixing a solution A and a solution B to obtain a suspension, wherein the solution A is a mixed solution of sodium ferrocyanide and sodium chloride, the solution B is a mixed solution of a doping source and a complexing agent, and the molar ratio of the sodium ferrocyanide to the doping source is 1-3;
(2) and (2) carrying out solid-liquid separation on the suspension obtained in the step (1), taking the solid and drying to obtain the cathode material.
6. The preparation method according to claim 5, wherein the mass concentration of sodium chloride in the suspension in the step (1) is 1 wt% to 10 wt%.
7. The method according to claim 5, wherein the concentration of sodium ferrocyanide in the solution A in the step (1) is 0.02mol/L-0.2 mol/L.
8. The method according to claim 5, wherein the sodium ferrocyanide of step (1) is sodium ferrocyanide decahydrate.
9. The method according to claim 5, wherein the solvent of the solution A in the step (1) is water.
10. The method according to claim 9, wherein the solvent of the solution A in the step (1) is deionized water.
11. The method according to claim 5, wherein the doping source in step (1) is a divalent transition metal salt.
12. The method according to claim 11, wherein the divalent transition metal salt comprises a divalent transition metal chloride and/or a divalent transition metal sulfate.
13. The method according to claim 11, wherein the divalent transition metal salt comprises any one or a combination of at least two of manganese salt, cobalt salt, nickel salt, copper salt, zinc salt, or ferrous salt.
14. The method according to claim 5, wherein the concentration of the doping source in the solution B in the step (1) is 0.02mol/L to 0.2 mol/L.
15. The method according to claim 5, wherein the complexing agent in step (1) comprises any one or a combination of at least two of sodium citrate, ethylenediamine tetraacetic acid, acetic acid, and sulfosalicylic acid.
16. The preparation method according to claim 5, wherein the molar ratio of the complexing agent to the doping source in the step (1) is 1:1-2: 1.
17. The method according to claim 5, wherein the solvent in the solution B in the step (1) is water.
18. The method according to claim 17, wherein the solvent in the solution B in the step (1) is deionized water.
19. The method according to claim 5, wherein the temperature of the mixing operation in the step (1) is 25 ℃ to 70 ℃.
20. The method according to claim 5, wherein the mixing in step (1) is carried out under stirring.
21. The method of claim 20, wherein the stirring is at a rate of 300rpm to 1000 rpm.
22. The method according to claim 5, wherein the mixing operation of step (1) is dropwise addition of the solution A and the solution B to the aqueous solution.
23. The method of claim 22, wherein the aqueous solution is water.
24. The method of claim 22, wherein the dropping rate of the solution a and the dropping rate of the solution B are independently 0.1mL/min to 1 mL/min.
25. The production method according to claim 24, wherein the dropping speed of the solution a and the dropping speed of the solution B are the same.
26. The method according to claim 5, wherein the step (1) further comprises: and carrying out hydrothermal reaction on the suspension.
27. The method of claim 26, wherein the hydrothermal reaction is carried out at a temperature of 150 ℃ to 200 ℃.
28. The method of claim 26, wherein the hydrothermal reaction is carried out for a time of 15h to 24 h.
29. The method of claim 26, wherein the hydrothermal reaction is performed in a hydrothermal kettle.
30. The production method according to claim 5, wherein in the step (2), the solid-liquid separation is centrifugal separation or suction filtration separation.
31. The method of claim 5, wherein step (2) further comprises: solid-liquid separation was performed by washing with water before drying to obtain a solid.
32. The production method according to claim 5, wherein in the step (2), the drying is performed in a vacuum drying oven.
33. The method according to claim 5, wherein the drying temperature in the step (2) is 100 ℃ to 120 ℃.
34. The method according to claim 5, wherein the drying time in the step (2) is 24 to 48 hours.
35. The production method according to claim 5, wherein in the step (2), the degree of vacuum for drying is 10mTorr to 15 mTorr.
36. The method for preparing according to claim 5, characterized in that it comprises the following steps:
(1) under the stirring conditions of 25-70 ℃ and 300-1000 rpm, dropwise adding the solution A and the solution B into water at a dropwise adding speed of 0.1-1.0 mL/min, wherein the dropwise adding speed of the solution A is the same as that of the solution B, and after the solution A and the solution B are completely dropwise added, placing the obtained suspension into a hydrothermal kettle for hydrothermal reaction at 150-200 ℃ for 15-24 h to obtain a suspension after the hydrothermal reaction; the solution A is a mixed solution formed by dissolving sodium ferrocyanide decahydrate and sodium chloride into water, the solution B is a mixed solution formed by dissolving a doping source and a complexing agent into water, and the doping source is divalent transition metal chloride and/or divalent transition metal sulfate;
(2) carrying out centrifugal separation or suction filtration separation on the suspension obtained after the hydrothermal reaction in the step (1), taking a solid, and drying the obtained solid in a vacuum drying oven at 100-120 ℃ and under the vacuum degree of 10mTorr-15mTorr for 24-48 h to obtain the cathode material;
wherein, in the suspension liquid in the step (1), the mass concentration of sodium chloride is 1 wt% -10 wt%; in the solution A, the concentration of the sodium ferrocyanide is 0.02-0.2 mol/L; in the solution B, the concentration of divalent transition metal ions is 0.02mol/L-0.2mol/L, and the molar ratio of the complexing agent to the divalent transition metal ions is 1:1-2: 1; in the system formed by mixing the solution A and the solution B, the molar ratio of the sodium ferrocyanide to the divalent transition metal ions is 1-3.
37. Use of the positive electrode material according to any one of claims 1 to 4, wherein the positive electrode material is used for a positive electrode of a solid-state sodium-ion battery.
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