CN115594224A - Recovery of waste liquid from production of lithium/sodium ion battery positive electrode material, obtained material and application - Google Patents
Recovery of waste liquid from production of lithium/sodium ion battery positive electrode material, obtained material and application Download PDFInfo
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Abstract
The invention relates to a method for recovering waste liquid from the production of a lithium/sodium ion battery anode material, and an obtained material and application thereof, wherein sodium sulfate waste liquid formed in the preparation process of a lithium/sodium ion battery layered oxide anode material is used as a raw material for preparing a sodium ferrous sulfate anode material for a sodium ion battery, and the PH of the solution is adjusted to be neutral by dilute sulfuric acid from the wastewater after ammonia removal, so that a high-purity sodium sulfate solution is obtained; adding a proper amount of ferrous sulfate and an antioxidant into the sodium sulfate solution to obtain a mixed solution; taking a proper amount of carbon source to be uniformly dispersed in the mixed solution to obtain a precursor solution; further carrying out spray drying on the precursor solution to obtain precursor powder; heat treating the precursor powder in inert gas atmosphere at 300-400 deg.C to obtain Na 2+2x Fe 2‑x (SO 4 ) 3 And C, a product. Compared with the prior art, the method has the advantages that the waste liquid generated in the production of the layered oxide cathode material is reasonably recycled, so that the problem of waste liquid treatment is solved, and the cathode material of the sodium-ion battery with high economic value is obtained. Has good application prospect.
Description
Technical Field
The invention belongs to the field of preparation of sodium-ion battery materials, and particularly relates to a recycling method of production waste liquid of a lithium/sodium-ion battery positive electrode material, and an obtained material and application thereof.
Background
Along with the rapid development of economy and continuous deepening of industrial degree in China, the demand of people on energy is increased day by day, and the problem of increasingly serious resource exhaustion of traditional fossil energy represented by coal, petroleum and natural gas is faced. In the above background, it is of great importance to the development and utilization of renewable clean energy sources such as solar energy, wind energy, tidal energy. Secondary battery energy storage represented by lithium ion batteries has the advantages of high energy density, long cycle life and the like, and is rapidly developed in the fields of electric vehicles and energy storage. However, with the rapid increase of the demand of people for lithium ion batteries, the problems of lithium resource shortage, uneven distribution and the like become increasingly prominent. Sodium, an element of the same main group as lithium, has similar physical and chemical properties, but sodium naturally abundantly reaches 2.75% in the earth's crust, is nearly 400 times that of lithium, and has relatively balanced resource distribution. Therefore, there is an extremely important strategic importance in the vigorous development of the related art of sodium ion batteries.
The positive electrode material is one of the key components of the lithium/sodium ion battery and mainly comprises three categories, namely layered oxides, polyanion compounds and prussian blue analogues. Among them, the problem that prussian blue analogues absorb moisture easily in the air, and the problem that polyanionic compounds have low compacted density have certain influence on their commercial application. The energy density of the layered transition metal oxide positive electrode material is high, and the layered transition metal oxide positive electrode material has gradually started to be in the commercialization stage. The preparation process of the layered transition metal oxide of the lithium/sodium ion battery is similar, in the production process, the preparation process of the precursor material of the layered transition metal oxide is carried out by adding a precipitator sodium carbonate or sodium hydroxide and the like to convert transition metal sulfate into insoluble carbonate or hydroxide for precipitation, and the remained waste liquid contains a large amount of sodium ions and sulfate ions, carbonate ions or hydroxide ions, a very small amount of transition metal ions and the like except a complexing agent. The pH value of the waste liquid is adjusted to further remove transition metal ions and carry out ammonia extraction treatment, the treated waste liquid is neutralized by sulfuric acid, and finally, the main component in the waste liquid is sodium sulfate which is directly discharged without being recycled, so that the waste of resources is caused, and serious water and soil pollution is caused. The traditional recovery method is to evaporate the sodium sulfate waste liquid to dryness, and the economic benefit of the recovered sodium sulfate product is not high. Therefore, it is commercially important to develop a recycling route with high economic efficiency.
The invention patent CN 106803588A also discloses a recycling method of sodium sulfate waste liquid, in the implementation of the method, hydrochloric acid is adopted to adjust the pH value of the sodium sulfate waste liquid to be neutral, then ferrous sulfate is added, the mixture is stirred at 80-100 ℃ to evaporate the solvent to dryness to obtain a precursor, and the precursor is subjected to heat treatment to obtain the ferrous sodium sulfate anode material. The above implementation method proposed by the patent of the invention has obvious problems: hydrochloric acid is adopted to adjust the PH value of the waste liquid to generate a large amount of NaCl byproducts, and inert NaCl is mixed in a sodium ferrous sulfate product to reduce the actual specific capacity of the product and Cl - The passivation layer of the aluminum foil is damaged, and the long-term cycle performance of the battery is affected. Namely, the sodium ferrous sulfate product obtained by the method is not suitable for being used in practical sodium ion batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recovering the production waste liquid of the lithium/sodium ion battery positive electrode material with high economic benefit, and the obtained material and application thereof.
The purpose of the invention can be realized by the following technical scheme: a method for recovering waste liquid generated in the production of a lithium/sodium ion battery positive electrode material comprises the following steps:
step S1: adjusting the pH value of the production waste liquid of the lithium/sodium ion battery anode material to 12-13, introducing hot steam or air for ammonia extraction, and adding dilute sulfuric acid into the waste liquid after ammonia extraction to adjust the pH value to be neutral to obtain a sodium sulfate solution; the waste liquid produced in the production process of the lithium/sodium ion battery positive electrode material is the waste liquid produced in the production process of the conventional lithium/sodium ion battery layered oxide positive electrode material, and the waste liquid contains a large amount of sodium ions, sulfate ions and the like. The ammonia extraction treatment is a conventional air stripping deamination treatment process in the field, and generally comprises the steps of feeding hot steam or air from the bottom of an air stripping tower, heating sewage, and separating free ammonia from the sewage after the temperature reaches a certain value.
Step S2: adding a proper amount of ferrous sulfate into the solution to ensure that the molar ratio of elements in the solution is sodium: iron: sulfur = 2.7-3; meanwhile, introducing inert gas into the solution, adding an antioxidant to inhibit oxidation of ferrous ions, and fully stirring to obtain a mixed solution;
and step S3: slowly adding a proper amount of carbon source into the mixed solution under the ultrasonic condition, and stirring for a period of time after the ultrasonic condition is finished to obtain a precursor solution;
and step S4: transferring the precursor solution to a spray dryer for spray granulation to obtain precursor powder;
step S5: and (3) placing the precursor powder obtained by spray drying in an inert atmosphere or a reducing atmosphere, and carrying out heat treatment to obtain the ferrous sodium sulfate cathode material.
Further, the inert gas in step S2 is one of argon and nitrogen.
Further, in the step S2, the antioxidant is one or more of ascorbic acid, iron wire, pyrrole and hydroquinone, and the molar amount of the antioxidant is 0-30% of the molar amount of the ferrous sulfate.
Further, in the step S3, the carbon source is one or more of graphene, graphene oxide, carbon nanotubes, carbon fibers and activated carbon, and the adding amount of the carbon source is 1% to 15% of the total mass of the mixture of ferrous sulfate and sodium sulfate.
Further, the ultrasonic treatment time in the step S3 is 20-40min, and the stirring time is 20-40min.
Further, the drying method of the precursor solution adopts a spray drying technology.
Further, the inert atmosphere in step S5 is one of argon, nitrogen, an argon-hydrogen mixed gas, and a nitrogen-hydrogen mixed gas.
Further, the heat treatment process in step S5 is: heating to 200 deg.C at 1-5 deg.C/min, maintaining for 0-12h, heating to 300-400 deg.C at 1 deg.C/min, and maintaining for 7-24h.
The invention also provides a method for preparing the lithium/sodium ionThe sodium ferrous sulfate anode material is obtained by a method for recovering production waste liquid of the anode material of the sub-battery, and the composition of the sodium ferrous sulfate anode material is Na 2+2x Fe 2-x (SO 4 ) 3 /C(x＝0.35～0.5)。
The invention also provides an application of the ferrous sodium sulfate anode material obtained by the method for recovering the production waste liquid of the lithium/sodium ion battery anode material, and the application of the ferrous sodium sulfate as the sodium ion battery anode material in the sodium ion battery is as follows: the positive pole piece is prepared by taking sodium ferrous sulfate as a positive active material, super P as a conductive agent and PVDF as a binder and applied to a sodium ion battery.
Na of Alluadite structure 2+2x Fe 2-x (SO 4 ) 3 As a polyanion-type anode material, the average working voltage is above 3.6V, the raw material source is wide, the preparation cost is low, the production process is energy-saving and environment-friendly, and the polyanion-type anode material has higher economic value and is one of the candidates of the commercial sodium-ion battery anode material. However, the materials have poor conductivity, and oxidation easily occurs in the preparation process, so how to effectively inhibit the oxidation of ferrous ions while realizing efficient carbon recombination is the key to prepare high-performance sodium ferrous sulfate. The carbon-based material can be embedded into Na by adding the carbon-based material into the reactant 2 Fe(SO 4 ) 2 In the body structure, substance particles are connected in series, a large number of charge transfer channels are provided, the charge transfer distance is shortened, and the internal conductivity of the material is obviously improved. In addition, the selected carbon-based material can be directly used as a carbon source to exert conductivity without high-temperature carbonization, so that the problem of poor conductivity of the material caused by insufficient carbonization is avoided. Compared with the prior art, the invention has the following beneficial effects:
1. the invention obtains the high-purity sodium sulfate solution by simply adjusting the pH value of the production waste liquid of the sodium ion battery anode material, and prepares the sodium ferrous sulfate product with high added value by taking the high-purity sodium sulfate solution as the raw material. The route has the advantages that firstly, the pollution problem caused by direct discharge of the production waste liquid of the material is effectively avoided, and secondly, the economic benefit caused by recycling the waste liquid is greatly improved while the waste liquid treatment cost is reduced.
2. The invention adopts the aqueous solution stirring-spray drying-low temperature calcining process with simple procedures, is easy for industrial popularization and realizes the large-scale production of the anode material. Compared with the traditional ball milling route, the method can directly adopt hydrated ferrous sulfate as a raw material, does not need to dehydrate in advance, and can realize the uniform mixing of the raw material in a molecular scale by stirring in an aqueous solution.
3. According to the invention, the antioxidant is added into the reactant, so that the oxidation of ferrous ions in the preparation process is effectively inhibited, the generation amount of inactive impurities in the calcination process is reduced, and the purity of the final product is improved. In addition, part of the antioxidants can also be used as carbon sources to realize in-situ carbon coating on the surface of the material in the subsequent calcining process.
4. According to the invention, the carbon-based material is added into the reactant, the selected carbon-based material can directly play a role of high conductivity without high-temperature carbonization, and the problem of poor conductivity of the material caused by insufficient carbonization of the traditional carbon source is solved. The conductive carbon-based material can be embedded into a sodium ferrous sulfate particle structure, a large number of charge transfer channels are provided, the charge transfer capacity is improved, and the conductivity inside the material particles and among the particles is obviously improved.
5. The invention provides a method for recycling sodium sulfate waste liquid formed in the production process of a layered transition metal oxide anode material as a raw material for producing a sodium ferrous sulfate anode material of a sodium ion battery. The implementation of the invention can generate good economic and social benefits, changes waste into valuable in the production of battery materials, solves the problem of wastewater treatment, saves the production cost, and is worthy of popularization and application.
Drawings
FIG. 1 shows Na prepared in example 1 2 Fe(SO 4 ) 2 The X-ray diffraction spectrum of the/C cathode material;
FIG. 2 shows Na prepared in example 1 2 Fe(SO 4 ) 2 Scanning electron micrographs of/C positive electrode material (30000 magnification);
FIG. 3 shows Na prepared in example 1 2 Fe(SO 4 ) 2 Charge-discharge curves of a sodium ion battery assembled by the/C positive electrode material under the multiplying power of 0.1C and 1C;
FIG. 4 shows Na prepared in example 1 2 Fe(SO 4 ) 2 A cycle performance diagram of a sodium ion battery assembled by the/C cathode material under the current density of 5C multiplying power;
FIG. 5 is Na prepared in comparative example 1 2 Fe(SO 4 ) 2 Charge and discharge curves at 0.1C rate for sodium ion batteries assembled with/C positive electrode materials.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
250mL of the ammonia extraction treated production waste liquid of the layered positive electrode material precursor of the sodium-ion battery is taken, and sulfuric acid is slowly dripped into the production waste liquid until the pH value of the solution is 7, so that a sodium sulfate solution with higher purity is obtained. And detecting the concentration of sodium ions in the solution, further adding a ferrous sulfate solution with the same molar weight as the sodium sulfate into the obtained solution, introducing argon, adding ascorbic acid according to 20% of the molar weight of the ferrous sulfate, and stirring for 15min until the raw materials are uniformly mixed. And then, adding the carbon nanofiber dispersion liquid accounting for 4% of the theoretical mass of the product into the mixed solution, carrying out ultrasonic treatment for 30min, transferring to a stirring table, and continuously stirring for 30min to obtain black mixed feed liquid.
And (3) carrying out spray granulation on the black feed liquid by using a spray dryer at an inlet temperature of 220 ℃, an air inlet speed of 80% and a feeding speed of 10% to obtain precursor powder.
Heating the precursor powder to 200 ℃ at a speed of 1 ℃/min in an argon atmosphere, preserving heat for 3h, then continuously heating to 350 ℃ at a speed of 1 ℃/min, preserving heat for 12h, and obtaining Na 2 Fe(SO 4 ) 2 a/C black powder product.
As shown in FIG. 1, na prepared in example 1 2 Fe(SO 4 ) 2 The X-ray diffraction pattern of the/C anode material; it can be seen from the figure that the prepared sample belongs to 212 type sodium ferrous sulfate compound with an Alluaudite structure, and the molecular formula is Na 2 Fe(SO 4 ) 2 The good crystallinity of the sample indicates that the method of the invention can successfully prepare Na with high crystallinity 2 Fe(SO 4 ) 2 And C, a positive electrode material.
FIG. 2 shows Na prepared in example 1 2 Fe(SO 4 ) 2 Scanning electron micrographs of/C positive electrode material (30000 magnification); it can be seen from the figure that the particle size of the obtained cathode material is 1-2.5 microns, and the particle size of most particles is relatively fine.
Na obtained by the above method 2 Fe(SO 4 ) 2 The positive electrode is formed by mixing the positive electrode active material/C, super P and PVDF in a mass ratio of (7); electrolyte 1mol/L NaClO4-EC/PC (1) 5% fec, glass fiber membrane as separator, metal sodium sheet as negative electrode, and button cell assembled in glove box with water oxygen below 0.01 ppm:
in the voltage range of 2.0-4.5V for Na prepared in example 1 2 Fe(SO 4 ) 2 And carrying out charge and discharge tests on the sodium ion battery with the/C composite material as the positive electrode. As shown in FIG. 3, na prepared in example 1 2 Fe(SO 4 ) 2 The charge-discharge curves of the sodium ion battery assembled by the/C cathode material under the multiplying power of 0.1C and 1C show that the discharge specific capacity of the obtained product under the current density of 0.1C is about 77.0mAh/g and reaches 84.6 percent of the theoretical capacity. And the discharge capacity at the rate of 1C can still reach 71mAh/g, which is 92.2% of the discharge capacity at the rate of 0.1C, and the material has good conductivity.
FIG. 4 shows Na prepared in example 1 2 Fe(SO 4 ) 2 The cycle performance of the sodium-ion battery assembled by the/C cathode material under the current density of 5C multiplying power can be seen from the figure, and the electricity at 5C can be seenThe capacity retention rate reaches 99.09 percent after 500 cycles of circulation under the current density, and almost no attenuation occurs, which shows that the material has excellent circulation stability.
Example 2
And taking 250mL of the production waste liquid of the layered positive electrode material precursor of the lithium ion battery after ammonia extraction treatment, and slowly dropwise adding sulfuric acid into the production waste liquid until the pH value of the solution is 7 to obtain a high-purity sodium sulfate solution. And detecting the concentration of sodium ions in the solution, further adding a ferrous sulfate solution with the molar weight ratio of 1.1 to the sodium sulfate into the obtained solution, introducing nitrogen, adding pyrrole according to 20% of the molar weight of the ferrous sulfate, and stirring for 15min until the raw materials are uniformly mixed. And then, adding the graphene oxide dispersion liquid accounting for 5% of the theoretical mass of the product into the mixed solution, carrying out ultrasonic treatment for 30min, and then continuing stirring for 30min to obtain black feed liquid.
And (3) carrying out spray granulation on the black feed liquid in a spray dryer at an inlet temperature of 220 ℃, an air inlet speed of 90% and a feeding speed of 10% to obtain precursor powder.
Heating the precursor powder to 200 ℃ at a speed of 1 ℃/min in an argon atmosphere, preserving heat for 3h, then continuously heating to 350 ℃ at a speed of 1 ℃/min, preserving heat for 12h, and obtaining Na 2 Fe 1.1 (SO 4 ) 2.1 a/C black powder product. Electrode tabs were prepared and button cells were assembled as in example 1.
In the voltage range of 2.0-4.5V for Na prepared in example 2 2 Fe 1.1 (SO 4 ) 2.1 And carrying out charge and discharge tests on the sodium ion battery with the/C composite material as the positive electrode. The specific discharge capacity of the obtained product at the current density of 0.1C is about 79.0mAh/g.
Example 3
And taking 250mL of the ammonia extraction treated sodium ion battery layered oxide positive electrode material production waste liquid, and slowly dropwise adding sulfuric acid into the waste liquid until the pH value of the solution is 7 to obtain a high-purity sodium sulfate solution. And detecting the concentration of sodium ions in the solution, further adding a ferrous sulfate solution with the molar weight ratio of 1.2 to the sodium sulfate into the obtained solution, introducing argon, adding 0.01mol of iron wires, and stirring for 15min until the raw materials are uniformly mixed.
And adding the carbon nano tube dispersion liquid accounting for 5% of the theoretical mass of the product into the mixed solution, performing ultrasonic treatment for 30min, and then continuing stirring for 30min to obtain black feed liquid.
And (3) carrying out spray granulation on the black feed liquid in a spray dryer at an inlet temperature of 220 ℃, an air inlet speed of 90% and a feeding speed of 10% to obtain precursor powder.
Heating the precursor powder to 200 ℃ at a speed of 1 ℃/min in an argon atmosphere, preserving heat for 3h, then continuously heating to 350 ℃ at a speed of 1 ℃/min, preserving heat for 12h, and obtaining Na 2 Fe 1.2 (SO 4 ) 2.2 C black powder product. The product was used to prepare an electrode sheet by the method of example 1, and a battery was assembled.
In the voltage range of 2.0-4.5V for Na prepared in example 3 2 Fe 1.2 (SO 4 ) 2.2 And carrying out charge and discharge tests on the sodium ion battery with the/C composite material as the positive electrode. The specific discharge capacity of the obtained product at the current density of 0.1C is about 80.0mAh/g.
Comparative example 1
And taking 250mL of the ammonia extraction treated sodium ion battery layered oxide positive electrode material production waste liquid, and slowly dropwise adding sulfuric acid into the waste liquid until the pH value of the solution is 7 to obtain a high-purity sodium sulfate solution. And detecting the concentration of sodium ions in the solution, further adding a ferrous sulfate solution with the same molar weight as the sodium sulfate into the obtained solution, introducing argon, and uniformly stirring to obtain a light green solution.
And (3) carrying out spray granulation on the light green solution in a spray dryer at an inlet temperature of 220 ℃, an air inlet speed of 80% and a feeding speed of 10% to obtain precursor powder.
Heating the precursor powder to 200 ℃ at a speed of 1 ℃/min in an argon atmosphere, preserving heat for 3h, then continuously heating to 350 ℃ at a speed of 1 ℃/min, preserving heat for 12h, and obtaining Na 2 Fe(SO 4 ) 2 And (3) powder. And electrode tabs were prepared and batteries were assembled as in example 1.
In the voltage range of 2.0-4.5V for Na prepared in the comparative example 1 2 Fe(SO 4 ) 2 And (3) carrying out charge and discharge tests on the sodium ion battery taking the material as the positive electrode.
FIG. 5 is Na prepared in comparative example 1 2 Fe(SO 4 ) 2 According to the charge-discharge curve of the sodium ion battery assembled by the cathode material under the multiplying power of 0.1C, the discharge specific capacity of the obtained product under the current density of 0.1C is about 10mAh/g, and the comparison result shows that the prepared sample has poor conductivity and the electrochemical performance is difficult to exert because no conductive agent is added in the sample preparation process in the comparison example. In the preparation process of the sodium ferrous sulfate electrode material, a proper amount of conductive carbon-based material is added into the mixed liquid of the sodium sulfate waste liquid and the ferrous sulfate, and in the prepared product, the added conductive carbon-based material forms a conductive network inside the active sodium ferrous sulfate particles and among the particles, so that the efficient charge transfer in the process of electrochemically inserting and removing sodium ions of the material is ensured, and the sodium storage activity of the sodium ferrous sulfate electrode material is effectively exerted.
Claims (10)
1. A method for recovering waste liquid generated in the production of a lithium/sodium ion battery positive electrode material is characterized by comprising the following steps:
step S1: adding dilute sulfuric acid into the production waste liquid after ammonia extraction treatment to adjust the pH value to be neutral, so as to obtain a sodium sulfate solution;
step S2: adding a proper amount of ferrous sulfate into the solution to ensure that the molar ratio of elements in the solution is sodium: iron: sulfur = 2.7-3; meanwhile, introducing inert gas into the solution, adding an antioxidant to inhibit oxidation of ferrous ions, and fully stirring to obtain a mixed solution;
and step S3: slowly adding a carbon source into the mixed solution under an ultrasonic condition, and stirring to obtain a precursor solution after the ultrasonic operation is finished;
and step S4: transferring the precursor solution to a spray dryer for spray granulation to obtain precursor powder;
step S5: and (3) placing the precursor powder obtained by spray drying in an inert atmosphere, and carrying out heat treatment to obtain the conductive carbon modified ferrous sodium sulfate composite anode material.
2. The method for recovering the waste liquid generated in the production of the positive electrode material of the lithium/sodium ion battery according to claim 1, wherein the inert gas in the step S2 is one of argon and nitrogen.
3. The method for recovering the waste liquid generated in the production of the positive electrode material of the lithium/sodium ion battery as claimed in claim 1, wherein the antioxidant in step S2 is one or more of ascorbic acid, iron wire, pyrrole and hydroquinone, and the molar amount of the antioxidant is 0-30% of the molar amount of the ferrous sulfate.
4. The method for recycling the waste liquid generated in the production of the positive electrode material of the lithium/sodium ion battery according to claim 1, wherein the carbon source in the step S3 is one or more of graphene, graphene oxide, carbon nanotubes, carbon fibers and activated carbon, and the amount of the added carbon source is 1-15% of the total mass of the mixture of ferrous sulfate and sodium sulfate.
5. The method for recovering the production waste liquid of the positive electrode material of the lithium/sodium ion battery as claimed in claim 1, wherein the ultrasonic treatment time of the step S3 is 20-40min, and the stirring time is 20-40min.
6. The method for recovering the waste liquid generated in the production of the positive electrode material of the lithium/sodium-ion battery according to claim 1, wherein the drying method of the precursor solution adopts a spray drying technology.
7. The method for recovering the waste liquid generated in the production of the positive electrode material of the lithium/sodium ion battery according to claim 1, wherein the inert atmosphere in the step S5 is one of argon, nitrogen, an argon-hydrogen mixed gas and a nitrogen-hydrogen mixed gas.
8. The method for recovering the waste liquid generated in the production of the positive electrode material of the lithium/sodium ion battery according to claim 1, wherein the heat treatment process in the step S5 comprises the following steps: heating to 200 deg.C at 1-5 deg.C/min, maintaining for 0-6h, heating to 300-400 deg.C at 1 deg.C/min, and maintaining for 7-24h.
9. The sodium ferrous sulfate cathode material obtained by the method for recovering the waste liquid generated in the production of the cathode material of the lithium/sodium ion battery according to claim 1, wherein the composition of the sodium ferrous sulfate cathode material is Na 2+2x Fe 2-x (SO 4 ) 3 /C(x＝0.35～0.5)。
10. The application of the ferrous sodium sulfate anode material obtained by the method for recovering the production waste liquid of the lithium/sodium ion battery anode material according to claim 9 is characterized in that the ferrous sodium sulfate as the sodium ion battery anode material is applied to the sodium ion battery.
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| CN116553621A (en) * | 2023-06-27 | 2023-08-08 | 深圳先进技术研究院 | Sodium iron sulfate and preparation method and application thereof |
| CN117720132A (en) * | 2024-02-07 | 2024-03-19 | 四川易纳能新能源科技有限公司 | Sodium iron sulfate and preparation method and application thereof |
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| CN116553621A (en) * | 2023-06-27 | 2023-08-08 | 深圳先进技术研究院 | Sodium iron sulfate and preparation method and application thereof |
| CN116553621B (en) * | 2023-06-27 | 2023-11-28 | 深圳先进技术研究院 | Sodium iron sulfate and preparation method and application thereof |
| CN117720132A (en) * | 2024-02-07 | 2024-03-19 | 四川易纳能新能源科技有限公司 | Sodium iron sulfate and preparation method and application thereof |
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