CN115893513B - Ternary sodium-electricity material modified by water molecule layer expansion and preparation method thereof - Google Patents
Ternary sodium-electricity material modified by water molecule layer expansion and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion battery materials, and discloses a ternary sodium electric material modified by a water molecule diffusion layer and a preparation method thereof. The invention firstly prepares the ternary manganese-based sodium-electricity anode material by adopting a coprecipitation method and a solid phase sintering method, then disperses the ternary manganese-based sodium-electricity anode material in water, and introduces CO 2 And (3) pressurizing and stirring the gas to react, and drying and dehydrating to obtain the ternary sodium-electricity material of the expansion layer. In the aqueous solution, sodium element in the material is partially removed, and meanwhile, water molecules enter the inside of the material structure, so that a multi-site defect and a water molecule diffusion layer structure are formed inside the ternary material. The preparation method has the advantages of simple process and low cost, and the prepared ternary sodium-electricity material has complete structure, uniform size and excellent electrochemical performance after the layer expansion.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery manufacturing, and particularly relates to a ternary sodium electric material modified by a water molecule diffusion layer and a preparation method thereof.
Background
The manganese-based sodium-electricity material has become the sodium-electricity anode material with the most development prospect due to the advantages of high stability, low cost and the like. The multi-metal doped manganese-based ternary material is similar to a lithium battery ternary material, and has a more stable structure and electrochemical performance than a sodium manganate material. However, as the ionic radius of sodium ions is much larger than that of lithium ions, the ternary manganese-based material formed after doping has higher electrochemical capacity and better rate capability. But a larger volume expansion is still unavoidable. To solve this problem, structural optimization of the material by structural engineering is required.
Generally, researchers can carry out structural modification on materials through surface coating and element doping, so that the structural stability is improved, but the surface coating is difficult to form a uniform protective layer, and doping elements are difficult to uniformly distribute. The synthesis process of the modification strategies is difficult to repeat, the synthesis conditions are difficult to unify, and the exploration of a structure modification method which is easy to operate, regulate and control and has good effect is still a difficult problem.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background technology, and provides a water molecule spread-layer modified ternary sodium-electricity material and a preparation method thereof.
In order to solve the problems of electrode degradation and lower ion transmission rate of the ternary sodium-electricity material in the electrochemical process and improve the structural stability and ionic electron conductivity of the material, the invention provides the technical scheme that: ternary sodium electric material modified by water molecule layer expansion, and molecular formula of ternary sodium electric material before layer expansion modification is Na x Mn (1-m) N m O 2 Wherein N consists of two of Fe, ni, co, cu, x is more than or equal to 0.6 and less than or equal to 1, m is more than or equal to 0.1 and less than or equal to 0.5, and the molecular formula of the ternary material after the expansion modification is Na y Mn (1-m) N m O 2 ·nH 2 O, wherein y is more than or equal to 0.4 and less than or equal to 1, and n is more than or equal to 0.01 and less than or equal to 0.5.
The sodium element in the ternary sodium electric material before modification is subjected to chemical reaction with CO2 molecules in an aqueous solution and is dissolved in the aqueous solution, so that the ternary sodium electric material before modification forms a positive electrode material with sodium defects, and water molecules are diffused into the ternary material structure before the expansion modification through the dual effects of pressure and molecular diffusion, so that the ternary sodium electric material after the water molecule expansion modification is formed.
A preparation method of a ternary sodium electric material modified by water molecule layer expansion comprises the following steps:
(1) Dissolving stoichiometric manganese salt and doped metal salt in deionized water to prepare metal salt solution, adding the metal salt solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding NaOH precipitant and NH 3 ·H 2 O complexing agent, pH value of the solution is regulated, and after coprecipitation reaction for a certain time, the solution is washed by water and alcoholWashing and drying to obtain a hydroxide precursor, ball-milling and mixing the hydroxide precursor and a sodium source, and sintering at a high temperature after uniform mixing to obtain the ternary sodium-electricity material before the expansion modification;
the high-temperature sintering temperature is 850-1200 ℃ and the sintering time is 10-30h. (2) Dispersing the ternary sodium-electricity material before the expansion layer modification prepared in the step (1) in water, and introducing CO into the water 2 And (3) pressurizing the reactor, continuously stirring, reacting for a certain time, and placing the material in a drying oven for drying treatment to obtain the ternary sodium-electricity material after the expansion modification.
Further, the manganese salt and the doped metal salt in the step (1) are one or more of soluble nitrate, acetate, sulfate and oxalate; the concentration of the NaOH precipitant is 2-6mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The NH is 3 ·H 2 The concentration of the O complexing agent is 10-40wt%; the pH value of the solution is 10-12, and the coprecipitation reaction time is 10-30h.
Further, the sodium source used in the high-temperature sintering process in the step (1) is one or more of sodium carbonate, sodium hydroxide and sodium bicarbonate, and the hydroxide precursor is as follows: the molar ratio of metal elements in the sodium source is 1: (1.03-1.06).
Further, in the step (2), the ternary sodium-electric material before the diffusion layer modification: the mass ratio of water is 1: (10-50), preferably 1: (20-30), the water: CO 2 The volume ratio of (1): (0.5-1), preferably 1: (0.8-1).
Further, the pressure of the reactor in the step (2) is in the range of 0.5 to 2MPa, preferably 1 to 1.5MPa, and the pressure reaction time is 10 to 30 hours, preferably 15 to 20 hours.
Further, the drying temperature in the step (2) is 140-200 ℃, preferably 160-180 ℃, and the drying time is 10-20h, preferably 10-15h.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the ternary sodium-electricity material before the expansion modification is dispersed in the aqueous solution, CO2 gas is introduced, and then the pressurizing reaction is carried out, so that part of sodium element in the material is removed to form sodium carbonate or sodium bicarbonate which is dissolved in water, meanwhile, water molecules enter the inside of the material structure to form a large interlayer spacing in the structure, and sodium ions can be more quickly transmitted between the layers, so that the electrochemical dynamic performance of the material is improved.
(2) Through partial removal of sodium ions and partial intercalation of water molecules, a multi-metal site defect and a water molecule spread layer structure are formed in the ternary sodium-electric material, and the multi-defect site provides more electrochemical active sites; the water molecules in the structure can not only enlarge the interlayer spacing, but also maintain the stability of the structure in the reversible process and promote the rapid transmission of sodium ions.
(3) The preparation method has the advantages of simple preparation process, short flow, readily available raw materials, no generation of toxic and harmful substances in the preparation process, and easy realization of large-scale production.
Drawings
FIG. 1 is a schematic view showing the cycle performance of the product in example 1 of the present invention.
Detailed Description
Example 1
(1) NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
(2) Taking 5g of Na in (1) 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 The active material was dispersed in 100ml of waterStirring, and introducing CO into the water 2 The amount of the solution to be introduced was 100ml. Pressurizing the reactor to 1.5MPa, stirring and reacting for 20h, and drying at 180 ℃ for 12h to obtain the ternary sodium electric material Na with the modified expansion layer 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.1H 2 O。
Na is mixed with 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.1H 2 Mixing O, conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
As shown in fig. 1, after the battery assembly was aged for 12 hours, charge and discharge tests of different potentials were performed. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 130.7mAhg -1 The capacity retention was 91.2%.
Comparative example 1
NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
Na is mixed with 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 104.5mAhg -1 The capacity retention was 73.1%.
Example 2
(1) NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
(2) Taking 5g of Na in (1) 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 The active material was dispersed in 100ml of water and stirred, during which CO was continuously introduced into the water 2 The amount of the solution to be introduced was 100ml. Pressurizing the reactor to 1MPa, stirring and reacting for 20h, and drying at 180 ℃ for 12h to obtain the ternary sodium electric material Na with the modified expansion layer 0.63 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.08H 2 O。
Na is mixed with 0.63 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.08H 2 Mixing O, conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 121.8mAhg -1 The capacity retention was 85.2%.
Example 3
(1) NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
(2) Taking 5g of Na in (1) 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 The active material was dispersed in 100ml of water and stirred, during which CO was continuously introduced into the water 2 The amount of the solution was 50ml. Pressurizing the reactor to 1.5MPa, stirring and reacting for 20h, and drying at 180 ℃ for 12h to obtain the ternary sodium electric material Na with the modified expansion layer 0.64 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.1H 2 O。
Na is mixed with 0.64 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.1H 2 Mixing O, conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling the metal sodium into slices, and blanking into 14mm round sodiumThe sheet served as a negative electrode with 1mol/L NaClO 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 119.0mAhg -1 The capacity retention was 83.2%.
Example 4
(1) NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
(2) Taking 5g of Na in (1) 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 The active material was dispersed in 100ml of water and stirred, during which CO was continuously introduced into the water 2 The amount of the solution to be introduced was 100ml. Pressurizing the reactor to 1.5MPa, stirring and reacting for 20h, and drying at 160 ℃ for 12h to obtain the ternary sodium electric material Na with the modified expansion layer 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.13H 2 O。
Na is mixed with 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.13H 2 Mixing O with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, taking N-methylpyrrolidone (NMP) as a solvent, and placing in a small beaker at a rotating speed of 800r/minStirring and mixing for 2h to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 124.1mAhg -1 The capacity retention was 86.8%.
Example 5
(1) NiSO is carried out 4 ·7H 2 O，CoSO 4 ·6H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:2:6 to be prepared into 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, and Ni is prepared through full reaction 0.2 Co 0.2 Mn 0.6 (OH) 2 A precursor. Taking 0.5mol Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 Precursor and 0.3mol Na 2 CO 3 Fully ball milling and mixing, sintering in a muffle furnace at 900 ℃ for 12 hours to obtain Na 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 An active material.
(2) Taking 5g of Na in (1) 0.67 Ni 0.2 Co 0.2 Mn 0.6 O 2 The active material was dispersed in 100ml of water and stirred, during which CO was continuously introduced into the water 2 The amount of the solution to be introduced was 100ml. Pressurizing the reactor to 1.5MPa, stirring and reacting for 20h, and thenDrying at 200 ℃ for 12 hours to obtain the ternary sodium electric material Na with modified expansion layer 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.08H 2 O。
Na is mixed with 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.08H 2 Mixing O, conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles of circulation at a current density of 1C under a voltage of 2-4.2V is 126.9mAhg -1 The capacity retention was 88.7%.
The performance comparison summary of the above examples and comparative examples is shown below:
comparison shows that when CO 2 The amount of the solution was 100ml. Pressurizing the reactor to 1.5MPa, and drying at 180 ℃ to obtain the amplified modified ternary sodium-electricity material Na 0.61 Ni 0.2 Co 0.2 Mn 0.6 O 2 ·0.1H 2 The O performance is most excellent.
The above description is only a basic description of the inventive concept, and any equivalent transformation according to the technical solution of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A ternary sodium-electric material modified by a water molecule expansion layer is characterized in that the molecular formula of the ternary sodium-electric material before the expansion layer modification is NaxMn (1-m) NmO, wherein N consists of two of Fe, ni, co, cu, x is more than or equal to 0.6 and less than or equal to 1, m is more than or equal to 0.1 and less than or equal to 0.5, and the molecular formula of the ternary material after the expansion layer modification is NayMn (1-m) NmO 2.nH2O, wherein y is more than or equal to 0.4 and less than or equal to 1, and N is more than or equal to 0.01 and less than or equal to 0.5;
the sodium element in the ternary sodium electric material before modification is subjected to chemical reaction with CO2 molecules in an aqueous solution and is dissolved in the aqueous solution, so that the ternary sodium electric material before modification forms a positive electrode material with sodium defects, and water molecules are diffused into the ternary material structure before the expansion modification through the dual effects of pressure and molecular diffusion, so that the ternary sodium electric material after the water molecule expansion modification is formed.
2. A method for preparing the ternary sodium-electric material modified by water molecule diffusion layer according to claim 1, which is characterized by comprising the following steps:
(1) Dissolving stoichiometric manganese salt and doped metal salt in deionized water to prepare a metal salt solution, adding the metal salt solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, adding a NaOH precipitant and a NH 3H 2O complexing agent, adjusting the pH value of the solution, performing coprecipitation reaction for a certain time, washing with water, washing with alcohol, drying to obtain a hydroxide precursor, ball-milling and mixing the hydroxide precursor with a sodium source, and performing high-temperature sintering after uniform mixing to obtain the ternary sodium-electricity material before the expansion modification;
the high-temperature sintering temperature is 850-1200 ℃ and the sintering time is 10-30h;
(2) Dispersing the ternary sodium electric material before the expansion modification prepared in the step (1) in water, introducing CO2 gas into the water, carrying out pressurized treatment on a reactor, continuously stirring, reacting for a certain time, and placing the material in a drying oven for drying treatment to obtain the ternary sodium electric material after the expansion modification.
3. The preparation method of the ternary sodium-electric material modified by water molecule diffusion layer according to claim 2, wherein the manganese salt and the doped metal salt in the step (1) are one or more of soluble nitrate, acetate, sulfate and oxalate; the concentration of the NaOH precipitant is 2-6mol/L; the concentration of the NH 3H 2O complexing agent is 10-40wt%; the pH value of the solution is 10-12, and the coprecipitation reaction time is 10-30h.
4. The preparation method of the ternary sodium-electric material modified by water molecule diffusion layer according to claim 2, wherein the sodium source used in the high-temperature sintering process in the step (1) is one or more of sodium carbonate, sodium hydroxide and sodium bicarbonate, and the hydroxide precursor is as follows: the molar ratio of metal elements in the sodium source is 1: (1.03-1.06).
5. The method for preparing a ternary sodium-electric material modified by a water molecule diffusion layer according to claim 2, wherein in the step (2), the ternary sodium-electric material before the diffusion layer modification is: the mass ratio of water is 1: (10-50), the water: the volume ratio of CO2 is 1: (0.5-1).
6. The method for preparing a ternary sodium electric material modified by water molecule diffusion layer according to claim 2, wherein the pressure of the reactor in the step (2) ranges from 0.5 to 2MPa, and the pressurizing reaction time ranges from 10 to 30 hours.
7. The method for preparing a ternary sodium electric material modified by water molecule diffusion layer according to claim 2, wherein the drying temperature in the step (2) is 140-200 ℃, and the drying time is 10-20h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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