CN115611321A - Method for preparing sodium ion battery positive electrode material by recycling waste battery positive electrode (nickel cobalt lithium manganate) and application - Google Patents
Method for preparing sodium ion battery positive electrode material by recycling waste battery positive electrode (nickel cobalt lithium manganate) and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a sodium ion battery anode material by recycling a waste battery anode (nickel cobalt lithium manganate) and application thereof. The result shows that the positive electrode material of the sodium-ion battery shows excellent sodium storage performance. The invention has simple operation process and controllable conditions; the waste power battery is used as a raw material, valuable components in the waste power battery are recycled, the environment is protected, resources are recycled, and high-value utilization of waste resources is realized; meanwhile, the transition metal elements can directly form layered transition metal oxides which are used for the positive electrode of the sodium-ion battery, and the regeneration and the conversion of resources are realized in a short process.
Description
Technical Field
The invention belongs to the technical field of waste battery regeneration, and particularly relates to a method for recycling and synthesizing a positive electrode material of a waste ternary lithium ion battery into a positive electrode material of a sodium ion battery.
Background
With the explosive increase of the number of electric vehicles, the first wave waste tide is about to come in 2019. Lithium ion power batteries have great recycling potential and market. Among the power batteries, a ternary battery and a lithium iron phosphate battery occupy the main positions, wherein the occupation ratio of the ternary battery is increased year by year. Lithium nickel cobalt manganese oxide (LiNi) is used for a ternary battery (NCM) x Co y Mn 1-x-y O 2 ) The power battery using the ternary material as the battery anode material contains a large amount of valuable metals. With the rapid development of new energy industry, global demand for high-value metals such as Co, ni and the like is increased rapidly, and the reserves of Co and Ni cannot meet the increasing exploitation amount, so that the future may face a serious shortage problem. Meanwhile, heavy metals such as Ni, co, mn and the like in the ternary power battery may pollute soil and underground water. Therefore, the research on the resource recycling technology of the waste ternary lithium ion battery has important significance and practical value.
Because the sodium has similar physical and chemical properties with the same group metal sodium of lithium, the reserves are richer, and the energy storage mechanism is similar, the sodium ion battery is one of the batteries which are most expected to replace the lithium ion battery to be applied to our lives. However, sodium ions have larger atomic radius than lithium ions, so most of the existing lithium ion battery cathode materials are not suitable for storing sodium, mainly because of the problems of small interlayer spacing, slow kinetics and the like.
Layered transition metal oxide Na x MeO 2 (Me represents transition metal) is an intercalation or intercalation compound, and compared with materials such as Prussian blue analogues, polyanion compounds and tunnel oxides, the layered transition metal oxide has higher specific capacity and meets the requirement of high energy density. According to Na + In MeO 6 The transition metal layer may be arranged in such a manner that Na is interposed between the transition metal layers x MeO 2 Is divided into O phase and P phase, wherein O phase is Na x MeO 2 Na in + Occupying MeO 6 Octahedral interstitial positions between the interlayers, na x MeO 2 In Na + Similar to LiCoO in diffusion path 2 A tetrahedral intermediate state that needs to go through a high energy state; and P phase Na x MeO 2 In Na + Occupying MeO 6 Triangular prism position between interlayers, na + The sodium ions are directly transmitted among the triangular prisms in a larger space, so that the sodium ions are relatively easy to diffuse.
Therefore, the layered transition metal oxide sodium ion battery positive electrode material is prepared by recycling the waste ternary power battery, and the transition metal oxide sodium electric positive electrode with a certain space structure is directly reconstructed by utilizing nickel, cobalt and manganese elements in the waste ternary power battery and adding a sodium source. The polymetallic oxide which is prepared by utilizing various metals in the waste ternary battery and contributes synergistically is used in the sodium-electricity anode, the original form of the nickel-cobalt lithium manganate is damaged, the interlayer spacing is enlarged, and the sodium ions are convenient to transmit and diffuse. The method is simple to operate, the conditions are controllable, valuable components in the waste power batteries are recycled, the rejection tide of the power batteries is facilitated to be solved, and the shortage of high-value metals is relieved; the result shows that the sodium ion battery cathode material has excellent sodium storage performance and application prospect.
Disclosure of Invention
The invention utilizes transition metal elements in waste commercial ternary batteries to extract valuable metals through leaching and coprecipitation, and sodium source is added to calcine the transition metal elements to convert the transition metal elements into layered transition metal oxide which can be used for a sodium ion anode. The invention aims to provide a method for preparing a layered metal oxide sodium ion battery anode material by recycling waste ternary power batteries, which has the advantages of simple process, strong operability, resource circulation and environmental protection.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a sodium ion battery anode material by recycling a waste battery anode (nickel cobalt lithium manganate) comprises the following steps:
the method comprises the following steps: acid leaching
Separating a certain amount of nickel cobalt lithium manganate (LiNi) x Co y Mn (1-x-y) O 2 ) The anode material is placed in sulfuric acid solution added with a certain amount of hydrogen peroxide, heated and stirred, dissolved fully, and added with a certain amount of NiSO 4 、CoSO 4 、MnSO 4 Adjusting the metal ratio; obtaining a metal sulfate solution;
step two: coprecipitation
Continuously introducing N into the metal sulfate solution obtained in the step one 2 Dropping ammonia water and NaOH solution into the metal sulfate solution, regulating pH to alkalinity, heating and stirring for a period of time to obtain precursor (Ni) x Co y Mn (1-x-y) OH 2 ) Precipitating;
step three: calcination of
(1) Taking ethanol as a dispersing agent, and mixing the precursor precipitate obtained in the step two with Na according to a certain proportion 2 CO 3 Mixing, and placing in a ball mill for ball milling for 2 to 4 hours to obtain a mixture;
(2) Placing the mixture obtained in the step (1) in an oven for fully drying;
(3) Placing the dried mixture in a muffle furnace at a temperature of 1-5% o Heating to 500-700 ℃ at the rate of C/min o Calcining for 5 to 8 hours, and then calcining for 1 to 5 o Heating to 900 to 1200 ℃ at the C/min rate o Calcining the mixture C for 10 to 15 hours to obtain layered nickel-cobalt-manganese oxide sodium (Na) z Ni x Co y Mn (1-x-y) O 2 ) A positive electrode material;
step four: application of positive electrode material of sodium-ion battery
And (3) taking the layered nickel-cobalt-manganese oxide material obtained in the step (3) as an active component of the positive electrode of the sodium ion battery, uniformly mixing and grinding the layered nickel-cobalt-manganese oxide material, a conductive agent carbon black and a binder PVDF according to the mass ratio of 8 6 the/EC/PC is electrolyte to assemble a button type 2025 battery.
The preparation method is characterized in that valuable metal components are recovered from a commercial ternary lithium ion battery, and then the high-performance sodium ion battery material is prepared.
The preparation method is characterized in that in the step one, the nickel cobalt lithium manganate (LiNi) as the anode material of the ternary battery x Co y Mn (1-x-y) O 2 ) The ternary material of the waste lithium ion power battery is recovered from new energy of mansion tungsten; lithium nickel cobalt manganese oxide (LiNi) as anode material of ternary battery x Co y Mn (1-x-y) O 2 ) Wherein x: y =1:1 or 5:2 or 6:2: or 8:1; the volume ratio of the hydrogen peroxide in the sulfuric acid solution added with a certain amount of hydrogen peroxide is 1-10 vol%, and the concentration of the sulfuric acid is 0.5-1.0 wt%; lithium nickel cobalt manganese (LiNi) x Co y Mn (1-x-y) O 2 ) The solid-liquid ratio of the material to sulfuric acid is 10 to 60 g/L, and the heating temperature is 40 to 80 o And C, the reaction time is 1 to 2 hours.
The preparation method is characterized in that in the second step, the concentrations of the ammonia water and the NaOH solution are both 0.5 to 2.0M, and the concentrations of the ammonia water and the NaOH solution are in a proportion of 1: 5363 and the metal sulfate solution is added dropwise in the mass ratio of 2~5, the pH of the solution is 10 to 11, and the temperature is 40 to 70 o Heating and stirring for 20 to 30 hours under the condition of C.
The preparation method is characterized in that in the third step, the precursor is mixed with Na 2 CO 3 The mixing mass ratio is 1:0.2 to 0.5.
The sodium ion battery prepared by the preparation method of the inventionThe anode material of the cell is a layered transition metal oxide (Na) z Ni x Co y Mn (1-x-y) O 2 ) Sodium electric material characterized by layered transition metal oxide (Na) z Ni x Co y Mn (1-x-y) O 2 ) Z =0.45, 0.67, or 0.8 in sodium electrical materials.
Specifically, a method for preparing a sodium ion battery positive electrode material by recycling a waste battery positive electrode (nickel cobalt lithium manganate), which comprises the following steps:
1. the method comprises the following steps: acid leaching
(1) Extracting the lithium nickel cobalt manganese oxide positive electrode: discharging and disassembling the 18650 ternary battery, and separating the inactivated nickel cobalt lithium manganate positive electrode material by an NMP dissolution method;
(2) Leaching: separating a certain amount of nickel cobalt lithium manganate (LiNi) x Co y Mn (1-x-y) O 2 ) Placing the mixture into a sulfuric acid solution added with a certain amount of hydrogen peroxide, heating and stirring the mixture, and fully dissolving the mixture to obtain a metal sulfate solution;
2. step two: coprecipitation
Continuously introducing N into the metal sulfate solution 2 Dropping ammonia water and NaOH solution into the metal sulfate solution, regulating pH to alkalinity, heating and stirring for a period of time to obtain precursor (Ni) x Co y Mn (1-x-y) OH 2 ) Precipitating;
3. step three: calcination of
(1) Ethanol is used as a dispersant, and the precursor precipitate is mixed with Na according to a certain proportion 2 CO 3 Mixing, and placing in a ball mill for ball milling for 2 to 4 hours to obtain a mixture;
(2) Placing the mixture in an oven for fully drying;
(3) Placing the dried mixture in a muffle furnace at a temperature of 1-5% o Heating to 500-700 ℃ at the rate of C/min o Calcining for 5 to 8 hours, and then calcining for 1 to 5 o Heating to 900 to 1200 ℃ at the C/min rate o Calcining the mixture C for 10 to 15 hours to obtain layered nickel-cobalt-manganese oxide sodium (Na) z Ni x Co y Mn (1-x-y) O 2 ) A positive electrode material;
4. step four: application of positive electrode material of sodium-ion battery
The newly synthesized layered nickel-cobalt-manganese oxide material is used as an active component of a positive electrode of a sodium ion battery, is uniformly mixed and ground with conductive agent carbon black and binder PVDF according to the mass ratio of 8 6 the/EC/PC is electrolyte to assemble a button type 2025 battery.
The positive electrode material (LiNi) of the ternary battery in the step one x Co y Mn (1-x-y) O 2 ) Wherein x: y =1:1 or 5:2 or 6:2: or 8:1, etc.;
in the first step, the lithium nickel cobalt manganese (LiNi) as the anode material of the ternary battery x Co y Mn (1-x-y) O 2 ) The ternary material of the waste lithium ion power battery is recovered from new energy of mansion tungsten; lithium nickel cobalt manganese oxide (LiNi) as anode material of ternary battery x Co y Mn (1-x-y) O 2 ) Wherein x: y =1:1 or 5:2 or 6:2: or 8:1; the volume ratio of the hydrogen peroxide in the sulfuric acid solution added with a certain amount of hydrogen peroxide is 1-10 vol%, and the concentration of the sulfuric acid is 0.5-1.0 wt%; lithium nickel cobalt manganese (LiNi) x Co y Mn (1-x-y) O 2 ) The solid-liquid ratio of the material to sulfuric acid is 10 to 60 g/L, and the heating temperature is 40 to 80 o C, reacting for 1 to 2 hours;
in the second step, the concentration of the ammonia water and the NaOH solution is 0.5 to 2.0M, and the ratio of 1: 5363 and the metal sulfate solution is added dropwise at the same time in the ratio of 2~5, the pH of the solution is 10 to 11, and the temperature is 40 to 70 o C, heating and stirring for 20 to 30 hours;
in the third step, the precursor is mixed with Na 2 CO 3 The mixing ratio is 1:0.2 to 0.5.
Compared with the prior art, the invention has the following advantages:
1. the method for recycling the waste ternary lithium ion battery anode material has the advantages of simple process, economy, feasibility, environmental protection and large-scale application.
2. The recycling method applies the waste ternary battery material to the sodium ion battery firstly, realizes short-process recycling and simultaneously manufactures the sodium ion battery anode material with excellent performance.
3. According to the method, the multi-metal oxide which is synergistically contributed by preparation of multiple metals in the ternary battery is used in the sodium-electricity anode, so that the original form of the nickel cobalt lithium manganate is damaged, the interlayer spacing is enlarged, sodium ions are conveniently transmitted and diffused, and the problems of small interlayer spacing, slow dynamics and the like of the anode material layer of the sodium-ion battery are solved.
Drawings
FIG. 1 shows the high performance layered Ni-Co-Mn oxide sodium positive electrode material Na obtained in examples 1 and 2 0.45 Ni 0.6 Co 0.2 Mn 0.2 O 2 /Na 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 XRD pattern of (a). In the figure, each peak at x =0.67 matches the hexagonal layered P2 type structure of the P63/mmc (No. 194) space group, and there is no hetero peak, indicating that a single-phase P2 type layered metal oxide is formed; as the Na content is reduced, the sample has additional diffraction peaks marked by middle stars, which correspond to the (111) (220) (311) (440) crystal planes of the spinel phase of the Fd-3m (No. 227) space group respectively, and shows that a small amount of the spinel phase is formed, and the P2 + Fd-3m composite material is formed.
FIGS. 2-a and 2-b show the high performance layered Ni-Co-Mn oxide sodium positive electrode materials Na obtained in example 1 and example 2, respectively 0.45 Ni 0.6 Co 0.2 Mn 0.2 O 2 And Na 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 SEM image of (d). As can be seen from the figure, when x =0.45, the product is a regular hexagonal sheet material accompanied by needle-point-shaped crystals, corresponding to a hexagonal phase and a spinel phase, indicating that a P2 + Fd-3m composite material is formed; when x =0.55/0.67, the material was mainly regular hexagonal plate-like crystals, indicating that the crystals were formed in a hexagonal crystal phase.
FIGS. 3 a and 3 b are diagrams showing the high-performance layered Ni-Co-Mn oxide electrode material Na obtained in example 1 0.45 Ni 0.6 Co 0.2 Mn 0.2 O 2 When the material is used as a positive electrode material of a sodium ion battery, a charge-discharge curve and a cycle performance graph under the low current density of 0.2C are shown; the charging and discharging curve shows 1.9V \3.6About V and 4.0V are provided with charge and discharge platforms which respectively correspond to the oxidation reduction of manganese, cobalt and nickel elements; at a current density of 0.2C, the capacity is kept at 100 mAh/g after 50 cycles, which shows that the material has a certain reversible capacity.
FIG. 4 shows the layered Ni-Co-Mn oxide material Na obtained in example 2 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 When the material is used as the positive electrode material of a sodium-ion battery, the concentration is 0.2 mV s -1 CV diagram under sweep speed, which shows oxidation-reduction peaks at 2.03 and 1.98V corresponding to tri-quadrivalent conversion of manganese element; the two redox peaks of (3.68)/3.65 correspond to the tri-tetravalent conversion of cobalt element, while the redox peaks above 4V correspond to the redox of nickel.
FIG. 5 shows the layered Ni-Co-Mn oxide material Na obtained in example 2 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 A rate performance graph when the material is used as a positive electrode material of a sodium ion battery; as can be seen from the figure, the material passes through 0.2C \0.5C \ 1C \
The circulation capacity of 2C \ 5C \ 10C returns to about 100 mAh/g, which indicates that the material has excellent rate capability.
FIGS. 6-a and 6-b show the high performance layered Ni-Co-Mn oxide material Na obtained in example 2 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 When the material is used as a positive electrode material of a sodium ion battery, the charge-discharge curve is under the low current density of 0.5C; as can be seen from the figure, the capacity of the material is maintained at 88 mAh/g after the material is circulated for 60 circles under the current density of 0.5C, and the capacity retention rate is 74.8%.
Detailed Description
Example 1
1) 4 g lithium nickel cobalt manganese oxide (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Place in 100mL add 4wt% H 2 O 2 In 1M sulfuric acid solution of (2), 60 o C heating and stirring 1 h to obtain the metal sulfate solution.
2) Continuously introducing nitrogen into the metal sulfate solution obtained in the step 1), simultaneously dropwise adding 1M ammonia water and 1M sodium hydroxide solution, and dropwise adding a solution prepared from the following components in a mass ratio of 1:5 until solution pH =10.2; maintaining solution pH =10.2,60 o C, heating and stirring for 24 hours; and filtering the precipitate and washing the precipitate to be neutral by ultrapure water to obtain the NCM precursor.
3) Drying with ethanol as dispersant to obtain NCM precursor and Na 2 CO 3 Mixing and ball-milling 4h, wherein the mixing mass ratio is 1:0.25, a mixture is obtained.
4) Placing the mixture obtained in step 3) at 80 o Oven-drying with C oven to obtain 12 h, and transferring to muffle furnace 5 o Heating to 500 deg.C/min o Calcining 5 h with 5C o Heating to 900 deg.C/min o Calcining 12 h by C to obtain the layered nickel-cobalt-manganese oxide sodium electrode (Na) 0.45 Ni x Co y Mn (1-x-y) O 2 ) And (3) a positive electrode material.
The layered nickel cobalt manganese oxide sodium electrode (Na) prepared in this example was used 0.45 Ni x Co y Mn (1-x-y) O 2 ) The active component serving as the positive electrode of the sodium-ion battery is uniformly mixed and ground with conductive agent carbon black and binder PVDF according to the mass ratio of 8 6 the/EC/PC is electrolyte to assemble a button type 2025 battery. All assemblies were performed in an inert atmosphere glove box and tested for cycle performance.
Example 2
1) 4 g lithium nickel cobalt manganese oxide (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Placed in 100ml with 4wt% H added 2 O 2 In 1M sulfuric acid solution of (2), 60 o C heating and stirring 1 h to obtain the metal sulfate solution.
2) Continuously introducing nitrogen into the sulfate solution, simultaneously dropwise adding 1M ammonia water and 1M sodium hydroxide solution according to the mass ratio of 1:5 until solution pH =10.2; maintaining solution pH =10.2, 60 o C, heating and stirring for 24 hours; and filtering the precipitate and washing the precipitate to be neutral by ultrapure water to obtain the NCM precursor.
3) Ethanol is used as a dispersing agent, and NCM precursor and Na are obtained after drying 2 CO 3 Mixing and ball-milling 4h, wherein the mixing mass ratio is 1:0.35.
4) Placing the mixture in 80 o Oven-drying with C oven to obtain 12 h, and transferring to muffle furnace 5 o Heating to 500 deg.C/min o Calcining 5 h with 5C o Heating to 900 deg.C/min o Calcining 12 h by C to obtain the layered Ni-Co-Mn oxide Na 0.67 Ni x Co y Mn (1-x-y) O 2 ) And (3) a positive electrode material.
The layered nickel cobalt manganese oxide sodium (Na) prepared by the present example was used 0.67 Ni x Co y Mn (1-x-y) O 2 ) The material is used as an active component of a positive electrode of a sodium ion battery, is uniformly mixed and ground with conductive agent carbon black and binder PVDF according to the mass ratio of 8 6 the/EC/PC is electrolyte to assemble a button type 2025 battery. All assemblies were performed in an inert atmosphere glove box and tested for cycle performance.
Example 3
1) 4 g lithium nickel cobalt manganese oxide (LiNi) 0.6 Co 0.2 Mn 0.2 O 2 ) Placed in 100ml with 4wt% H added 2 O 2 In 1M sulfuric acid solution of (1), 70 o C heating and stirring 1 h to obtain the metal sulfate solution.
2) Continuously introducing nitrogen into the sulfate solution, simultaneously dropwise adding 0.2M ammonia water and 1M sodium hydroxide solution until the pH of the solution is =10.2; maintaining solution pH =10.2, 60 o Heating and stirring under C for 24h; and filtering the precipitate and washing the precipitate to be neutral by ultrapure water to obtain the NCM precursor.
3) Drying with ethanol as dispersant to obtain NCM precursor and Na 2 CO 3 Mixing and ball-milling 3 h, wherein the mixing mass ratio is 1:0.35.
4) Placing the mixture at 90 o Oven-drying C10 h, and transferring to muffle 2 o The temperature rises to 600 ℃ at a rate of C/min o Calcining 4h with 2 o Heating to 900 deg.C/min o Calcining the mixture C by 10 h to obtain the layered nickel-cobalt-manganese oxide sodium electrode (Na) 0.67 Ni 0.6 Co 0.2 Mn 0.2 O 2 ) And (3) a positive electrode material.
Adopt this realityLayered nickel cobalt manganese oxide sodium electrode (Na) prepared in example 0.67 Ni x Co y Mn (1-x-y) O 2 ) The material is used as an active component of a positive electrode of a sodium ion battery, is uniformly mixed and ground with conductive agent carbon black and binder PVDF according to the mass ratio of 8 6 the/EC/PC is an electrolyte assembled into a button 2025 type battery. All assembly was carried out in an inert atmosphere glove box.
Example 4
1) 1 g lithium nickel cobalt manganese oxide (LiNi) 0.8 Co 0.1 Mn 0.1 O 2 ) Placed in 25 mL and added 4wt% H 2 O 2 60 in 1M sulfuric acid solution o C heating and stirring 1 h to obtain the metal sulfate solution.
2) Continuously introducing nitrogen into the sulfate solution, simultaneously dropwise adding 1M ammonia water and 1M sodium hydroxide solution according to the mass ratio of 1:5 until the solution pH =10.2; maintaining solution pH =10.2, 60 o Heating and stirring under C for 24h; and filtering the precipitate and washing the precipitate to be neutral by ultrapure water to obtain the NCM precursor.
3) Drying with ethanol as dispersant to obtain NCM precursor and Na 2 CO 3 Mixing and ball-milling 3 h, wherein the mixing mass ratio is 1:0.45.
4) Placing the mixture at 90 o Oven-drying C10 h, and transferring to muffle 1 o The temperature rises to 600 ℃ at a rate of C/min o Calcining 4h with 1 o Heating to 800 deg.C/min o Calcining 12 h by C to obtain the layered nickel-cobalt-manganese oxide sodium electrode (Na) 0.8 Ni 0.6 Co 0.2 Mn 0.2 O 2 ) And (3) a positive electrode material.
The layered nickel cobalt manganese oxide sodium electrode (Na) prepared in this example was used 0.67 Ni x Co y Mn (1-x-y) O 2 ) The material is used as an active component of a positive electrode of a sodium ion battery, is uniformly mixed and ground with conductive agent carbon black and binder PVDF according to the mass ratio of 8 6 the/EC/PC is electrolyte assemblyA button 2025 type battery. All assembly was carried out in an inert atmosphere glove box.
Claims (6)
1. A method for preparing a sodium ion battery anode material by recycling a waste battery anode (nickel cobalt lithium manganate) comprises the following steps:
the method comprises the following steps: acid leaching
Separating a certain amount of nickel cobalt lithium manganate (LiNi) x Co y Mn (1-x-y) O 2 ) The anode material is placed in sulfuric acid solution added with a certain amount of hydrogen peroxide for heating and stirring, is fully dissolved, and is added with a certain amount of NiSO 4 、CoSO 4 、MnSO 4 Adjusting the metal ratio; obtaining a metal sulfate solution;
step two: coprecipitation
Continuously introducing N into the metal sulfate solution obtained in the step one 2 Dropping ammonia water and NaOH solution into the metal sulfate solution, regulating pH to alkalinity, heating and stirring for a period of time to obtain precursor (Ni) x Co y Mn (1-x-y) OH 2 ) Precipitating;
step three: calcination of
Taking ethanol as a dispersing agent, and mixing the precursor precipitate obtained in the step two with Na according to a certain proportion 2 CO 3 Mixing, and placing in a ball mill for ball milling for 2 to 4 hours to obtain a mixture;
placing the mixture obtained in the step (1) in an oven for fully drying;
placing the dried mixture in a muffle furnace at a temperature of 1-5% o Heating to 500-700 ℃ at the rate of C/min o Calcining for 5 to 8 hours, and then calcining for 1 to 5 o Heating to 900 to 1200 ℃ at the C/min rate o Calcining the mixture C for 10 to 15 hours to obtain layered nickel-cobalt-manganese oxide sodium (Na) z Ni x Co y Mn (1-x-y) O 2 ) A positive electrode material;
step four: application of positive electrode material of sodium-ion battery
Taking the layered nickel-cobalt-manganese oxide material obtained in the step (3) as an active component of the positive electrode of the sodium-ion battery, and mixing the layered nickel-cobalt-manganese oxide material with a conductive agent carbon black and a binder PVDF according to a weight ratio of 8:1:1, uniformly coating the mixture on an aluminum foil as a working electrode after being mixed and ground according to the mass ratio of 1, taking a metal sodium sheet as a counter electrode, and 1 mol/L NaPF 6 the/EC/PC is electrolyte to assemble a button type 2025 battery.
2. The production method according to claim 1, characterized in that valuable metal components are recovered from a commercial ternary lithium ion battery, and then a high-performance sodium ion battery material is produced.
3. The method according to claim 1, wherein in the first step, the positive electrode material of the ternary battery is lithium nickel cobalt manganese oxide (LiNi) x Co y Mn (1-x-y) O 2 ) The ternary material of the waste lithium ion power battery is recovered from new energy of mansion tungsten; lithium nickel cobalt manganese oxide (LiNi) as anode material of ternary battery x Co y Mn (1-x-y) O 2 ) Wherein x: y =1:1 or 5:2 or 6:2: or 8:1; the volume ratio of the hydrogen peroxide in the sulfuric acid solution added with a certain amount of hydrogen peroxide is 1-10 vol%, and the concentration of the sulfuric acid is 0.5-1.0 wt%; lithium nickel cobalt manganese (LiNi) x Co y Mn (1-x-y) O 2 ) The solid-liquid ratio of the material to sulfuric acid is 10 to 60 g/L, and the heating temperature is 40 to 80 o And C, the reaction time is 1 to 2 hours.
4. The preparation method according to claim 1, wherein in the second step, the concentrations of the ammonia water and the NaOH solution are 0.5 to 2.0M, and the ratios of the ammonia water and the NaOH solution are 1: 5363 and the metal sulfate solution is added dropwise in the mass ratio of 2~5, the pH of the solution is 10 to 11, and the temperature is 40 to 70 o Heating and stirring for 20 to 30 hours under the condition of C.
5. The method according to claim 1, wherein in step three, the precursor is mixed with Na 2 CO 3 The mixing mass ratio is 1:0.2 to 0.5.
6. The positive electrode material of the sodium-ion battery prepared by the preparation method of any one of claims 1 to 5 is a layered transition metal oxide (Na) z Ni x Co y Mn (1-x-y) O 2 ) Sodium electric material characterized by layered transition metal oxide (Na) z Ni x Co y Mn (1-x-y) O 2 ) Z =0.45, 0.67, or 0.8 in sodium electrical materials.
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