CN115463935B - Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry - Google Patents
Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry Download PDFInfo
- Publication number
- CN115463935B CN115463935B CN202210835876.2A CN202210835876A CN115463935B CN 115463935 B CN115463935 B CN 115463935B CN 202210835876 A CN202210835876 A CN 202210835876A CN 115463935 B CN115463935 B CN 115463935B
- Authority
- CN
- China
- Prior art keywords
- iron
- lithium
- rich
- solid waste
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for preparing lithium battery cathode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry, which takes bulk iron-rich solid waste/hazardous waste of iron and steel enterprises-electric furnace dust removal ash, iron oxide red or iron scale as raw materials, oxalic acid as a leaching agent and iron powder as a reducing agent, and prepares high-purity ferrous oxalate by hydrothermal complexation leaching and hydrothermal reduction complexation precipitation; then, ferrous oxalate is used as a raw material, and lithium iron phosphate which is a lithium battery anode material with high purity and good physical and chemical properties is synthesized through a solid phase reaction, so that the aim of recycling, high-value and green low-cost utilization of the metallurgical large Zong Fu iron solid waste/hazardous waste is finally achieved. The technical scheme provided by the method has the advantages of short process flow, simple equipment, low reaction temperature and higher added value of products, and the prepared lithium iron phosphate positive electrode material of the lithium battery has the first reversible specific capacity of 146.43 mAh.g ‑1 After 20 times of circulation, the capacity retention rate is 100%, and the method has wide market prospect.
Description
Technical Field
The invention belongs to the technical field of high-value utilization of iron-rich solid waste in the metallurgical industry, and particularly relates to a method for preparing lithium iron phosphate serving as a positive electrode material of a lithium battery with high added value by green extraction of iron-containing solid waste in iron and steel enterprises, which is particularly suitable for mainly taking Fe as iron in iron-rich solid waste resources 3+ In the form of (a) the iron content is more than or equal to 40 percent, and the impurity element CaO, mgO, siO 2 、Al 2 O 3 The metallurgical iron-containing dust mud with the impurity content of organic matters and the like not higher than 15 percent is recycled.
Background
With the gradual depletion of non-renewable resources such as petroleum, coal, natural gas, etc., the development and utilization of new energy sources, such as nuclear energy, solar energy, electric energy, etc., are gradually becoming the focus development direction of research hotspots of scientific researchers and industry layout. Taking an inexpensive and convenient electrochemical energy storage device as an example, the lithium ion battery has the characteristics of long cycle life, high use safety and more environmental friendliness, and has very rapid application development. In 2020, the yield of lithium batteries in China reaches approximately 500 hundred million, and the yield is increased by more than 150% in a comparable way; the power battery yield reaches 217GWh, which is already the largest consumer end, and can reach 1000GWh even in 2025 years. The method not only provides great market application prospect for the development of lithium battery production technology, but also provides higher requirements and challenges for the improvement of the performance of lithium battery materials and the optimization control of the cost.
Taking the lithium ion battery as an example, the positive electrode material of the lithium ion battery often occupies a larger proportion than the negative electrode material. Therefore, the property of the positive electrode material of the lithium battery directly affects the performance of the lithium ion battery, and the positive electrode material of the lithium battery is formedThe cost of the whole set of battery is directly determined. In a batch of lithium battery positive electrode materials which are recently developed, the lithium iron phosphate has the advantages of large capacity, high temperature resistance, long service life, low price and the like, is widely applied to various high-capacity energy storage elements and high-power battery equipment, and is the energy storage material with the best comprehensive performance and the most application prospect at present. Along with the great development and utilization of the lithium iron phosphate material in the aspects of electric automobiles and energy storage batteries, the market scale and the market capacity of the lithium iron phosphate material can be further enlarged, and the popularization and application prospect is very wide. The method expands the applicable range of an iron source in the preparation of the lithium iron phosphate material, optimizes the preparation process of the lithium iron phosphate and is a key for solving the market problem and the cost problem. Most of solid waste resources generated by metallurgical enterprises have rich Fe resources, if the Fe resources can be used as raw materials for synthesizing the lithium iron phosphate, the problem of the impending solid waste treatment of the iron and steel enterprises can be solved, the production cost of the lithium iron phosphate can be greatly reduced from the source, and the social benefit and the economic benefit are obvious. Taking electric furnace dust as an example, the electric furnace dust contains a large amount of Fe and Zn resources, and the content of Fe (taking Fe as the raw material 2 O 3 Calculated) and Zn content (calculated by ZnO) can reach 40 percent and more than 10 percent respectively, and is a typical high Zong Futie hazardous waste. The main treatment mode at the present stage is mainly to be matched with a rotary hearth furnace or a rotary kiln for recycling, which not only causes serious waste of Fe and Zn resources, but also brings a series of serious environmental problems. The iron oxide red is a resource utilization product generated when iron and steel enterprises treat and dispose the iron and steel pickling waste liquid and waste steel slag, and the utilization of the iron oxide red is mainly used for preparing magnetic ferrite or pigment at present. However, the method has the defects of low added value, complex process flow, large acid and alkali consumption and the like, and is not suitable for large-scale production. The patent 'a method for preparing iron oxide red by using iron-containing waste and iron oxide red pigment' (CN 201810770162.1) provides a method for preparing iron oxide red by using iron-containing waste, which comprises the steps of firstly converting iron element in the iron-containing waste into ferric hydroxide or ferrous hydroxide by using excessive sodium hydroxide, and then preparing gamma-Fe by two-step drying under the condition of 400-800 ℃ in a closed environment 2 O 3 . However, the alkali consumption is high, the technological process is long, the product purity is low, and the initiative of enterprises for technical improvement is not positive. The patent 'a method for producing high-purity iron powder by utilizing iron slag' (CN 201711066037.4) provides a method for preparing high-purity iron powder by utilizing converter slag. Firstly adding iron slag into a soaking solution composed of sodium hydroxide, sodium methacrylate sulfonate and deionized water for impurity removal, placing filter residues into an electrolytic tank for electrolysis to prepare metal iron powder, and then placing the iron powder separated out on a cathode into an ethylenediamine tetraacetic acid solution for cleaning to remove impurity ions adsorbed on the surface, thereby finally obtaining the iron powder with the purity of more than 95%. However, the method has long process flow, large medicament consumption and large waste residue and waste liquid production, and restricts the further popularization and application of the technology to a certain extent.
In view of the above, the invention provides a method for preparing lithium iron phosphate as a positive electrode material of a lithium battery by utilizing the iron-rich solid waste resource of the existing iron and steel enterprises at a high value, aiming at the cost and the environmental problems faced by the prior iron-rich solid waste resource utilization technology. The method takes bulk iron-rich waste in the metallurgical industry as an initial raw material (such as iron oxide red, electric furnace dust, blast furnace dust and the like), oxalic acid as a leaching agent and iron powder as a reducing agent, and converts abundant iron resources into ferrous oxalate which is an important raw material for synthesizing lithium iron phosphate; and then, preparing a lithium battery anode material with high added value, namely lithium iron phosphate, by taking the prepared ferrous oxalate as an iron source for synthesizing lithium iron phosphate, ammonium dihydrogen phosphate as a phosphorus source, and lithium hydroxide or lithium carbonate as a lithium source through a solid-phase synthesis method. The method for recycling and high-value utilization of large amounts of iron-rich solid wastes in the metallurgical industry not only meets the treatment requirements of 'reduction, recycling and harmlessness' of the solid wastes, but also achieves the purposes of reducing the sources of the solid wastes and controlling the whole process of pollutants, and the produced high-added-value products can bring actual profits to enterprises, so that the method has very wide popularization and application values in the metallurgical industry.
Disclosure of Invention
The invention aims to overcome the defects of high roasting temperature, low added value of products, complex process flow, large amount of waste residue and waste liquid production and high production cost in the conventional process for treating iron-rich solid waste in the metallurgical industry, and provides the method for preparing the lithium iron phosphate serving as the lithium battery anode material from the iron-rich solid waste in the metallurgical industry, which has the advantages of short process flow, simple equipment, low reaction temperature, milder reaction condition, higher added value of products and small use amount of lithium sources, prepares ferrous oxalate through hydrothermal complexation, synthesizes the lithium iron phosphate serving as the lithium battery anode material with good physicochemical properties through solid phase reaction, and finally achieves the purposes of recycling and high-value utilization of large iron-containing solid waste in the metallurgical industry.
In order to achieve the purpose, the invention takes iron-containing solid waste generated in actual production activities of iron and steel enterprises as raw materials, oxalic acid as a leaching agent and iron powder as a reducing agent, and converts abundant iron into high-purity ferrous oxalate through hydrothermal complex leaching and hydrothermal reduction complex precipitation, so that the obtained ferrous oxalate is taken as a main raw material to prepare the lithium iron phosphate anode material with good physical and chemical properties. The method for preparing the lithium battery anode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry is implemented by the following steps:
1) Raw material preparation: the iron-rich dangerous/solid waste of iron and steel enterprises is used as a raw material, and is subjected to crushing and grinding operation treatment to obtain fine-grain iron-rich materials with the grain size of-0.074 mm being more than or equal to 80.0%, and the grain size of-0.074 mm being more than or equal to 90.0% is preferable.
If the water content of the raw materials is high, drying treatment is also carried out before crushing and grinding. After the fine-grain iron-rich material with proper grain size is obtained, the occurrence state and the content of Fe need to be clarified, so that a specific mode for comprehensively utilizing the Fe needs to be determined.
The iron-rich danger/solid waste of the iron and steel enterprises is generally solid waste such as electric furnace dust, iron oxide red, iron scale (steel rolling iron scale) and the like.
2) Extracting iron by hydrothermal complexation leaching: adding the fine-grain iron-rich material obtained in the step 1) and oxalic acid solution with designed concentration according to the calculated liquid-solid ratio, fully and uniformly mixing, placing the mixture into constant-temperature reaction equipment, regulating the reaction temperature and the reaction time to enable the iron oxide in the fine-grain iron-rich material to undergo hydrothermal complex reaction to generate Fe which is easy to dissolve in water and acid liquor(C 2 O 4 ) 3 3- And is free in solution; after the hydrothermal complex reaction is finished, solid-liquid separation is carried out on the reaction product, and the iron-rich complex ion leaching liquid I is obtained after multiple times of filtration, washing and purification.
The multiple times are 3 times or more. According to the difference of the raw materials in the step 1), the residual slag amount and the components after solid-liquid separation are different. If the step 1) adopts iron oxide red or iron scale as raw materials, the residue amount is small, and the iron oxide red or iron scale can be directly mixed into smelting furnace burden as ingredients; if step 1) adopts electric furnace dust as raw material, a larger amount of residue is produced, and the components in the residue are CaO, mgO, siO 2 、Al 2 O 3 Mainly, can be used as ingredients of ceramsite and building bricks; if the iron-rich solid waste is lead and zinc, the baking-free brick or the baked brick which meets the strength grade requirement of MU15 in solid concrete brick (GB/T21144-2007) and has leaching toxicity lower than the limit value requirement of hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007) is prepared after the curing and stabilizing method is adopted, or products such as ceramsite, baking-free brick and the like are prepared after valuable metal elements such as lead, zinc and the like are extracted, and finally, the full quantification and high-value comprehensive utilization of the iron-rich solid waste in metallurgical industry are realized.
3) Preparing ferrous oxalate by hydrothermal reduction complexing iron precipitation: taking the iron-rich complex ion leaching solution I obtained in the step 2) as a raw material, oxalic acid and reduced Fe powder as additives, controlling the reaction temperature, the raw material proportion and the reaction time, and separating out ferrous oxalate crystals from the solution at normal temperature and normal pressure; and carrying out solid-liquid separation on the separated ferrous oxalate crystals, and carrying out vacuum drying treatment to obtain high-purity ferrous oxalate powder with the purity of more than or equal to 98.0%.
4) Solid phase reaction to synthesize lithium iron phosphate: preparing a lithium iron phosphate precursor by taking the high-purity ferrous oxalate powder obtained in the step 3) as an iron source for synthesizing lithium iron phosphate, lithium carbonate/lithium hydroxide as a lithium source, ammonium dihydrogen phosphate as a phosphorus source and absolute ethyl alcohol as a medium; after the lithium iron phosphate precursor is obtained, a two-step solid phase synthesis method is adopted in a reducing roasting atmosphere, heat preservation is sequentially carried out at different roasting temperatures of 350-500 ℃ and 650-900 ℃ for 10-20 h and 20-32 h, and finally the lithium iron phosphate product meeting the performance requirements of the lithium battery anode material and having excellent electrochemical performance is obtained.
Further, iron in the iron-rich danger/solid waste of the iron and steel enterprises in the step 1) is expressed as Fe 2 O 3 Preferably, fe in the mixture 2 O 3 The iron in the alloy is preferably more than 30% of the total mass of the raw materials; preferably, the iron element is in the presence of Fe 3+ 、Fe 2+ With Fe 0 Wherein Fe is 3+ The content is preferably 70% or more of the total amount of Fe element.
Further, the liquid-to-solid ratio (ml/g) of oxalic acid to fine-grained iron-rich material in step 2) is preferably in the range of (10-40): 1, preferably (15-20): 1; the mass concentration of the oxalic acid solution is preferably 10-50%, preferably 20-25%; the reaction temperature is 50-95 ℃, preferably 70-85 ℃; the reaction time is 1 to 5 hours, preferably 1.5 to 2.5 hours.
Further, the mass ratio of oxalic acid added in the step 3) to Fe in the iron-rich complex ion leaching solution I is (0.5-2.5): 1, preferably (1.0-2.0): 1; the mass ratio of the reduced iron powder to Fe in the iron-rich complex ion leaching solution I is (3-4) 1, the reaction temperature is 60-90 ℃, and the preferable temperature is 75-85 ℃; the stirring speed is 300-400 r/min, and the reaction time is 2-3 h.
Further, in the step 3), in the vacuum drying treatment operation, the vacuum drying temperature is 50-80 ℃, preferably 60-70 ℃; the vacuum degree is 10.13 to 30.39kPa, preferably 10.13 to 20.26kPa; the drying time is 5 to 20 hours, preferably 8 to 12 hours.
Further, in the step 4), the mass ratio of the high-purity ferrous oxalate powder, the lithium carbonate/lithium hydroxide and the monoammonium phosphate is (2.0-2.5): 1: (2.0 to 2.5); the two-step solid phase synthesis method is adopted, and lithium iron phosphate is synthesized into two stages under the reducing roasting atmosphere: the first stage is preferably carried out at the roasting temperature of 400-450 ℃ for 12-15 h; on the basis of finishing the reaction in the first stage, continuously heating to 700-900 ℃ to enter the second stage, and preserving the heat for 24-28 h at the roasting temperature of 750-800 ℃ in the second stage.
Compared with the prior art, the method for preparing the lithium battery anode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry has the following advantages:
(1) The invention provides a method for preparing a high-added-value lithium battery anode material lithium iron phosphate by wet treatment of large iron-rich solid wastes in the metallurgical industry, and finally achieves recycling and high-value utilization of the large Zong Fu iron solid wastes, belonging to the original innovative technology. The process eliminates the defects of high roasting temperature and amplified discharge of the traditional treatment process, utilizes the iron-containing solid waste as a raw material, eliminates the pollution to the ecological environment, and reduces the raw material cost of the lithium iron phosphate serving as the anode material of the lithium battery. From the whole technical process, the unit production cost can be reduced by more than 50%, and the economic advantage is obvious;
(2) The invention provides a method for preparing lithium iron phosphate as a positive electrode material of a lithium battery by using iron-rich solid waste in the metallurgical industry. Compared with the conventional technology, the reaction mother liquor is returned to the pre-reaction process for recycling, and the byproduct is not required to be neutralized, so that the discharge of wastewater is greatly reduced while a large amount of alkali liquor required by the neutralization reaction is saved, and the environmental protection treatment cost can be reduced by more than 60 percent as a whole; the process route is simple and controllable, the yield can reach more than 90 percent, and the method is suitable for industrial mass production;
(3) The invention provides a method for recycling and high-value utilization of bulk iron-rich solid wastes in the metallurgical industry. Combining the characteristics of lithium iron phosphate materials, adopting iron-containing solid waste in the metallurgical industry as a raw material, and selecting different reaction conditions to prepare ferric oxalate powder with the particle size of 0.5-10 mu m, wherein the particle size is completely controllable; the purity of the product is more than 98.5 percent, the highest purity can reach 99.5 percent, the product meets the requirements of downstream battery production enterprises on the quality of the product, the added value of the product is higher, and the product has more competitiveness in the market;
(4) The invention provides a method for preparing a high value added product lithium iron phosphate by taking bulk iron-rich solid in the metallurgical industry as a raw material and recycling and utilizing the iron-rich solid at a high value. The preparation cost can be reduced by 60-70% from the whole production process flow of lithium iron phosphate, the technical and economic value is high, and compared with the traditional process, the method has more industrialization prospect; the reaction condition is mild, part of the traditional production process flow is simplified, the investment is saved, and the direct economic benefit is obvious.
(5) The lithium iron phosphate of the lithium battery anode material prepared by the method has the first reversible specific capacity of 146.43 mAh.g -1 After 20 times of circulation, 146.63 mAh.g is still maintained -1 The capacity retention was 100%, indicating that it has excellent cycle stability.
(6) Assembled 2025 button cell was subjected to electrochemical testing: the charge and discharge curves of the front and the back times are basically coincident, which shows that LiFePO 4 Has good cycle stability in the charge and discharge process.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a lithium battery cathode material lithium iron phosphate by using iron-rich solid wastes in the metallurgical industry;
FIG. 2 is a XRD diffraction pattern of prepared ferrous oxalate powder from iron-containing solid waste iron oxide red of iron and steel enterprises according to the method of the present invention, wherein the diffraction angle 2 theta of the adopted Cu-K alpha target radiation is 10-90 ℃, and the X-ray wavelength lambda= 0.15416nm;
FIG. 3 is a diffraction spectrum of a prepared lithium iron phosphate powder XRD using iron-containing solid waste iron oxide red of iron and steel enterprises as an initial raw material, using Cu-K alpha target radiation, wherein the diffraction angle 2 theta is 10-90 ℃, and the X-ray wavelength lambda= 0.15416nm;
FIG. 4 is a XRD diffraction pattern of prepared ferrous oxalate powder by using iron-containing hazardous waste electric furnace dust of iron and steel enterprises as raw materials, wherein the diffraction angle 2 theta of the prepared Cu-K alpha target radiation is 10-90 ℃, and the wavelength lambda= 0.15416nm of X rays;
FIG. 5 is a diffraction spectrum of lithium iron phosphate powder XRD prepared by using iron-containing hazardous waste electric furnace dust of iron and steel enterprises as an initial raw material according to the method of the invention, wherein the adopted Cu-K alpha target radiates at a diffraction angle 2 theta of 10-90 ℃ and has X-ray wavelength lambda= 0.15416nm;
FIG. 6 is a graph of the charge and discharge curves of the first three times of constant current charge and discharge tests performed on a prepared lithium iron phosphate material at a current density of 0.1C;
FIG. 7 is a graph of 2.5 to 4.2V (vs. Li/Li + ) The cycling performance curve of the lithium iron phosphate material was experimentally prepared over a range of potentials at a current density of 0.1C.
Detailed Description
For describing the invention, the method for preparing the lithium battery anode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry is further described in detail below with reference to the accompanying drawings and examples.
As shown in a process flow chart of a method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in the metallurgical industry, the method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in the metallurgical industry is implemented by adopting the following steps:
1) Raw material preparation: iron-rich danger/solid waste of iron and steel enterprises, namely electric furnace dust, iron oxide red or iron scale, are taken as raw materials, and are dried, crushed and ground to obtain fine-grained iron-rich materials with the grain size fraction of-0.074 mm of more than or equal to 90.0%; the occurrence state of iron element in the selected raw materials is Fe 3+ 、Fe 2+ With Fe 0 And is made of Fe 2 O 3 Mainly, wherein Fe 2 O 3 The iron in the alloy is more than 30 percent of the total mass of the raw materials, fe 3+ The content is preferably 70% or more of the total amount of Fe element.
2) Extracting iron by hydrothermal complexation leaching: adding the fine-grain iron-rich material obtained in the step 1) and oxalic acid solution with the mass concentration of 20-25%, according to the liquid-solid ratio (ml/g) of oxalic acid to the fine-grain iron-rich material (15-20): 1, fully and uniformly mixing, placing the mixture into constant-temperature reaction equipment, and carrying out a hydrothermal complexing reaction on iron oxide in the fine-grain iron-rich material at the reaction temperature of 70-85 ℃ for 1.5-2.5 hours to generate Fe (C) which is easy to dissolve in water and acid liquor 2 O 4 ) 3 3- And is free in solution; after the hydrothermal complex reaction is finished, solid-liquid separation is carried out on the reaction product, and the iron-rich complex ion leaching liquid I is obtained after multiple times of filtration, washing and purification.
3) Preparing ferrous oxalate by hydrothermal reduction complexing iron precipitation: taking the iron-rich complex ion leaching solution I obtained in the step 2) as a raw material, oxalic acid and reduced Fe powder as additives, and controlling the reaction temperature, the raw material proportion and the reaction time, namely: the mass ratio of the added oxalic acid to the Fe in the iron-rich complex ion leaching solution I is (1.0-2.0): 1, the mass ratio of the reduced iron powder to the Fe in the iron-rich complex ion leaching solution I is (3-4): 1, the reaction temperature is 75-85 ℃, the stirring speed is 300-400 r/min, and the reaction time is 2-3 h; separating out ferrous oxalate crystals from the solution at normal temperature and normal pressure; and carrying out solid-liquid separation on the precipitated ferrous oxalate crystals, and carrying out vacuum drying treatment at the vacuum drying temperature of 60-70 ℃ and the vacuum degree of 10.13-20.26 kPa for 8-12 hours to obtain the high-purity ferrous oxalate powder with the purity of more than or equal to 98.5%.
4) Solid phase reaction to synthesize lithium iron phosphate: taking the high-purity ferrous oxalate powder obtained in the step (3) as an iron source for synthesizing lithium iron phosphate, taking lithium carbonate/lithium hydroxide as a lithium source, taking ammonium dihydrogen phosphate as a phosphorus source, and taking absolute ethyl alcohol as a medium to prepare a lithium iron phosphate precursor; after obtaining the lithium iron phosphate precursor, adopting a two-step solid phase synthesis method under a reducing roasting atmosphere, and sequentially carrying out heat preservation at different roasting temperatures of 400-450 ℃ and 750-800 ℃ for 12-15 h and 24-28 h, thereby finally obtaining the lithium iron phosphate product meeting the performance requirements of the lithium battery anode material. In the step, the mass ratio of the high-purity ferrous oxalate powder, lithium carbonate/lithium hydroxide and ammonium dihydrogen phosphate is (2.0-2.5): 1: (2.0-2.5).
The invention will be described in detail with reference to the following specific examples:
example 1:
(1) 1g of iron oxide red which is a typical bulk solid waste of a martensitic steel company is weighed, dried, crushed and ground, and then screened by a 200-mesh sieve, and the granularity of more than 90% of samples in the raw materials is controlled to be less than or equal to-0.074 mm.
(2) Mixing the ore sample obtained in the step (1) with 20% oxalic acid solution, wherein the liquid-solid ratio is 20:1, fully and uniformly mixing to form uniform slurry, and then placing the uniform slurry into constant-temperature water bath equipment, wherein the reaction conditions are specifically set as follows: the leaching temperature is 85 ℃, the reaction time is 2 hours, and the stirring speed is set to 400r/min; after the hydrothermal complex reaction is finished, carrying out solid-liquid separation on the reaction product to obtain iron-rich complex ion leaching solution I, and fixing the volume of the iron-rich complex ion leaching solution I to 250mL; at this time, it was found from the ICP-AES analysis that the concentration of Fe in the leachate I was 2572mg/L.
(3) The leaching liquid I in the arrangement is used as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: 1.08g of oxalic acid and 2.02g of reduced iron powder are added, the leaching temperature is 85 ℃, the reaction time is 2 hours, and the stirring speed is 400r/min. After the reaction is finished, carrying out solid-liquid separation after the solution is cooled to room temperature, and vacuum drying the solid obtained by the filtration reaction for 12 hours under the conditions of 65 ℃ and the vacuum degree of 10.13kPa to finally obtain high-purity ferrous oxalate powder, wherein the XRD diffraction pattern of the reaction product is shown in figure 2; as can be seen from FIG. 2, the Cu-K alpha target radiation is used with a diffraction angle 2 theta of 10-90 deg.C and an X-ray wavelength lambda= 0.15416nm. As can be seen from fig. 2: compared with a ferrous oxalate standard card, the ferrous oxalate powder prepared by utilizing the ferric oxide red has good crystallization performance and high strength, and does not contain any impurity peak.
(4) The ferrous oxalate obtained in the step is used as a raw material, a solid phase reaction method is adopted, and the lithium iron phosphate is prepared through a two-step method, and the specific experimental conditions are as follows: 1.8g of ferrous oxalate, 0.37g of lithium carbonate and 1.5g of ammonium dihydrogen phosphate are respectively weighed, alcohol is adopted as a medium, and fully grinded to prepare a precursor; under the reducing roasting condition, firstly, preserving heat for 12 hours under the condition of 400 ℃; after the heat preservation is finished, heating is carried out immediately, and the heat preservation is continued for 24 hours under the experimental condition of 750 ℃; and after the reaction is finished, cooling the system, taking out a sample after the furnace body is cooled, and the XRD diffraction pattern of the reaction product is shown in figure 3. As can be seen from fig. 3, the cu—kα target radiation employed has a diffraction angle 2θ of 10 to 90 ℃ and an X-ray wavelength λ= 0.15416nm. As can be seen from fig. 3: compared with a standard card of lithium iron phosphate, the lithium iron phosphate powder prepared by utilizing the iron oxide red has good crystallization performance and high peak strength, and does not contain any impurity peak; further experimental examination revealed that the purity of the lithium iron phosphate powder at this time was 98.25%.
Example 2:
(1) 1g of iron-containing hazardous waste, namely electric furnace dust, which is typical of a horse steel company is weighed, dried, crushed and ground, and then is screened by a 200-mesh sieve, and the granularity of more than 90% of samples in the raw materials is controlled to be less than or equal to-0.074 mm.
(2) Mixing the ore sample obtained in the step (1) with 20% oxalic acid solution, wherein the liquid-solid ratio is 20:1, fully and uniformly mixing to form uniform slurry, and then placing the uniform slurry into constant-temperature water bath equipment, wherein the reaction conditions are specifically set as follows: the leaching temperature is 80 ℃, the reaction time is 2.5h, and the stirring speed is 400r/min; after the hydrothermal complex reaction is finished, carrying out solid-liquid separation on the reaction product to obtain iron-rich complex ion leaching solution I, and fixing the volume of the iron-rich complex ion leaching solution I to 250mL; at this time, it was found from the ICP-AES analysis that the concentration of Fe in the leachate I was 1575mg/L.
(3) The leaching liquid I in the arrangement is used as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: 0.64g of oxalic acid and 1.18g of reduced iron powder are added, the leaching temperature is 85 ℃, the reaction time is 2 hours, and the stirring speed is 400r/min. After the reaction is finished, the solution is cooled to room temperature for solid-liquid separation, the solid obtained by the filtration reaction is dried for 12 hours under the conditions of 65 ℃ and the vacuum degree of 10.13kPa, and finally the high-purity ferrous oxalate powder is obtained, and the XRD diffraction pattern of the reaction product is shown in figure 4. As can be seen from FIG. 4, the Cu-K alpha target radiation is used with a diffraction angle 2 theta of 10-90 deg.C and an X-ray wavelength lambda= 0.15416nm. As can be seen from fig. 4: compared with a ferrous oxalate standard card, the ferrous oxalate powder prepared by using the electric furnace dust-removing ash has good crystallization performance and high peak intensity, and does not contain any impurity peak.
(4) The ferrous oxalate obtained in the step is used as a raw material, a solid phase reaction method is adopted, and the lithium iron phosphate is prepared through a two-step method, and the specific experimental conditions are as follows: 1.2g of ferrous oxalate, 0.25g of lithium carbonate and 0.77g of ammonium dihydrogen phosphate are respectively weighed, alcohol is adopted as a medium, and fully grinded to prepare a precursor; under the reductive roasting condition, firstly, preserving heat for 12 hours at 450 ℃, then heating up immediately after the heat preservation is finished, and preserving heat for 24 hours at 750 ℃ under the experimental condition; and after the reaction is finished, cooling the system, taking out a sample after the furnace body is cooled, and the XRD diffraction pattern of the reaction product is shown in figure 5. As can be seen from FIG. 5, the Cu-K alpha target radiation is used with a diffraction angle 2 theta of 10-90 deg.C and an X-ray wavelength lambda= 0.15416nm. As can be seen from fig. 5: compared with a standard card of lithium iron phosphate, the lithium iron phosphate powder prepared by using the electric furnace dust removal ash has good crystallization performance and high peak intensity, and does not contain any impurity peak.
(5) To study LiFePO 4 In the electrochemical properties of LiFePO obtained in step (4) 4 The prepared pole piece is an active electrode, the metal lithium is a counter electrode, and the assembled 2025 button cell is subjected to electrochemical test: liFePO at a current density of 0.1C in the potential range of 2.5-4.2V (vs. Li/Li+) 4 Constant current charge and discharge tests were performed. Fig. 6 is a graph of the charge and discharge curves of the previous three times when constant current charge and discharge tests were performed on the prepared lithium iron phosphate material at a current density of 0.1C. As seen in fig. 6, liFePO 4 The specific capacities of the first charge and discharge of the battery are 142.17 mAh.g-1 and 146.47 mAh.g respectively -1 The first coulomb efficiency of the material is 103.0%; in addition, the charge and discharge curves of the second and third times are basically coincident, indicating LiFePO 4 Has good cycle stability in the charge and discharge process.
(6) To verify the cycling stability of the experimentally prepared lithium iron phosphate materials, the experiments subsequently determined a potential in the range of 2.5-4.2V (vs. Li/li+), liFePO prepared 4 The cycle performance curve at 0.1C current density, results are shown in fig. 7: as seen in fig. 6, liFePO 4 The first reversible specific capacity of (a) is 146.43 mAh.g -1 After 20 times of circulation, 146.63 mAh.g is still maintained -1 The capacity retention was 100%, indicating that it has excellent cycle stability.
Claims (10)
1. The method for preparing the lithium battery anode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry is characterized by comprising the following steps of:
1) Raw material preparation: taking iron-rich dangerous/solid waste of iron and steel enterprises as a raw material, and carrying out crushing and grinding operation treatment to obtain a fine-grain iron-rich material with the grain size of-0.074 mm and the content of more than or equal to 80.0%;
2) Extracting iron by hydrothermal complexation leaching: adding the fine-grain iron-rich material obtained in the step 1) and oxalic acid solution with designed concentration according to the calculated liquid-solid ratio, fully and uniformly mixing, placing the mixture into constant-temperature reaction equipment, regulating the reaction temperature and the reaction time to enable the iron oxide in the fine-grain iron-rich material to undergo hydrothermal complex reaction to generate water and acid solution which are easy to dissolveFe(C 2 O 4 ) 3 3- And is free in solution; after the hydrothermal complex reaction is finished, carrying out solid-liquid separation on a reaction product, and obtaining an iron-rich complex ion leaching solution I after multiple times of filtration, washing and purification;
3) Preparing ferrous oxalate by hydrothermal reduction complexing iron precipitation: taking the iron-rich complex ion leaching solution I obtained in the step 2) as a raw material, oxalic acid and reduced Fe powder as additives, controlling the reaction temperature, the raw material proportion and the reaction time, and separating out ferrous oxalate crystals from the solution at normal temperature and normal pressure; separating solid from liquid of the separated ferrous oxalate crystals, and performing vacuum drying treatment to obtain high-purity ferrous oxalate powder with purity more than or equal to 98.0%;
4) Solid phase reaction to synthesize lithium iron phosphate: preparing a lithium iron phosphate precursor by taking the high-purity ferrous oxalate powder obtained in the step 3) as an iron source for synthesizing lithium iron phosphate, lithium carbonate/lithium hydroxide as a lithium source, ammonium dihydrogen phosphate as a phosphorus source and absolute ethyl alcohol as a medium; after the lithium iron phosphate precursor is obtained, a two-step solid phase synthesis method is adopted in a reducing roasting atmosphere, heat preservation is sequentially carried out at different roasting temperatures of 350-500 ℃ and 650-900 ℃ for 10-20 h and 20-32 h, and finally the lithium iron phosphate product meeting the performance requirements of the lithium battery anode material is obtained.
2. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 1, wherein the method comprises the following steps: iron in iron-rich danger/solid waste of iron and steel enterprises in step 1) is expressed as Fe 2 O 3 Mainly, wherein Fe 2 O 3 The iron in the steel accounts for more than 30% of the total mass of the raw materials.
3. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 1, wherein the method comprises the following steps: the occurrence state of iron element in the raw material is Fe 3+ 、Fe 2+ With Fe 0 Wherein Fe is 3+ The content of the Fe element is more than 70 percent of the total content of the Fe element.
4. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 1, 2 or 3, wherein the method comprises the following steps: the liquid-solid ratio (ml/g) of oxalic acid and fine iron-rich material in the step 2) is (10-40): 1, the mass concentration of oxalic acid solution is 10-50%, the reaction temperature is 50-95 ℃ and the reaction time is 1-5 h.
5. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 4, wherein the method comprises the following steps: the liquid-solid ratio (ml/g) of oxalic acid and fine iron-rich material in the step 2) is (15-20): 1, the mass concentration of oxalic acid solution is 20-25%, the reaction temperature is 70-85 ℃ and the reaction time is 1.5-2.5 h.
6. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 5, wherein the method comprises the following steps: the mass ratio of oxalic acid added in the step 3) to Fe in the iron-rich complex ion leaching solution I is (0.5-2.5): 1, the mass ratio of reduced iron powder to Fe in the iron-rich complex ion leaching solution I is (3-4): 1, the reaction temperature is 60-90 ℃, the stirring speed is 300-400 r/min, and the reaction time is 2-3 h.
7. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 6, wherein the method comprises the following steps: the mass ratio of oxalic acid added in the step 3) to Fe in the iron-rich complex ion leaching solution I is (1.0-2.0): 1, the mass ratio of reduced iron powder to Fe in the iron-rich complex ion leaching solution I is (3-4): 1, and the reaction temperature is 75-85 ℃.
8. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 7, wherein the method comprises the following steps: in the vacuum drying treatment operation, the vacuum drying temperature is 50-80 ℃, the vacuum degree is 10.13-30.39 kPa, and the drying time is 5-20 hours.
9. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 8, wherein the method comprises the following steps: in the vacuum drying treatment operation, the vacuum drying temperature is 60-70 ℃, the vacuum degree is 10.13-20.26 kPa, and the drying time is 8-12 hours.
10. The method for preparing the lithium battery cathode material lithium iron phosphate by using the iron-rich solid waste in the metallurgical industry as claimed in claim 9, wherein the method comprises the following steps: in the step 4), the mass ratio of the high-purity ferrous oxalate powder, the lithium carbonate/lithium hydroxide and the ammonium dihydrogen phosphate is (2.0-2.5): 1: (2.0 to 2.5); the first stage is to keep the temperature at the roasting temperature of 400-450 ℃ for 12-15 h, and the second stage is to keep the temperature at the roasting temperature of 750-800 ℃ for 24-28 h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111198498.3A CN113787085A (en) | 2021-10-14 | 2021-10-14 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
| CN2021111984983 | 2021-10-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115463935A CN115463935A (en) | 2022-12-13 |
| CN115463935B true CN115463935B (en) | 2023-07-28 |
Family
ID=79185056
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111198498.3A Pending CN113787085A (en) | 2021-10-14 | 2021-10-14 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
| CN202210836286.1A Pending CN115532770A (en) | 2021-10-14 | 2022-07-15 | Method for preparing lithium ion battery anode material lithium iron phosphate by using iron scale as raw material |
| CN202210835876.2A Active CN115463935B (en) | 2021-10-14 | 2022-07-15 | Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111198498.3A Pending CN113787085A (en) | 2021-10-14 | 2021-10-14 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
| CN202210836286.1A Pending CN115532770A (en) | 2021-10-14 | 2022-07-15 | Method for preparing lithium ion battery anode material lithium iron phosphate by using iron scale as raw material |
Country Status (3)
| Country | Link |
|---|---|
| CN (3) | CN113787085A (en) |
| WO (1) | WO2023060889A1 (en) |
| ZA (1) | ZA202302411B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113787085A (en) * | 2021-10-14 | 2021-12-14 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
| CN114315255B (en) * | 2022-01-27 | 2023-03-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for preparing high-purity alloy by using electric furnace dust removal ash and recycling tailings |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08152124A (en) * | 1994-11-28 | 1996-06-11 | Ishikawajima Harima Heavy Ind Co Ltd | Decomposition method of molten salt in incinerated ash melting furnace |
| JPH108150A (en) * | 1996-06-21 | 1998-01-13 | Tama Kagaku Kogyo Kk | Combustion treatment of waste material coated and deposited with metallic foil of secondary battery |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
| WO2014056143A1 (en) * | 2012-10-09 | 2014-04-17 | 上海交通大学 | Lithium iron phosphate material and preparation thereof |
| CN103746115A (en) * | 2013-12-13 | 2014-04-23 | 灵宝金源矿业股份有限公司 | Method for preparing cell-grade lithium iron phosphate from pyrite slag |
| WO2015006796A1 (en) * | 2013-07-17 | 2015-01-22 | Technological Resources Pty. Limited | Treatment of minerals |
| CN105129761A (en) * | 2015-08-31 | 2015-12-09 | 无锡市嘉邦电力管道厂 | Method for preparing ferrous phosphate positive pole material |
| CN110112481A (en) * | 2019-04-23 | 2019-08-09 | 北京科技大学 | Waste lithium iron phosphate battery recycles the method for preparing lithium iron phosphate positive material |
| CN110256235A (en) * | 2019-07-26 | 2019-09-20 | 攀枝花学院 | A method of ferrous oxalate is prepared using vanadium slag |
| CN110306044A (en) * | 2019-07-18 | 2019-10-08 | 北京科技大学 | A kind of method of the hydro-thermal oxalic acid complexation leaching vanadium iron spinelle containing vanadium in vanadium mineral |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4158706B2 (en) * | 2003-01-14 | 2008-10-01 | 三菱マテリアル株式会社 | Processing method and manufacturing method for separating gold from platinum group-containing solution |
| WO2009015565A1 (en) * | 2007-07-31 | 2009-02-05 | Byd Company Limited | Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery |
| CN102084034B (en) * | 2008-04-11 | 2012-12-12 | 弗朗索瓦·卡达雷利 | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| CL2009002156A1 (en) * | 2009-12-03 | 2010-03-05 | Biosigma Sa | Hydrometallurgical procedure for the production of ferric sulfate in iron concentration greater than 20g / l, and with contents less than 1 g / l of silicon and other impurities, in which said process is carried out in three stages: leaching of phyalitic slags, removal of impurities and bioxidation of ferrous solution in bioreactor. |
| CN102719668B (en) * | 2012-07-09 | 2014-12-17 | 山东理工大学 | Technology for extracting zinc, lead and silver step by step by processing zinc-leached residues by full wet process |
| WO2014012258A1 (en) * | 2012-07-20 | 2014-01-23 | 深圳市德方纳米科技有限公司 | Auto-thermal evaporative liquid-phase synthesis method for cathode material for battery |
| JP6392650B2 (en) * | 2014-12-03 | 2018-09-19 | Ｄｏｗａメタルマイン株式会社 | Rare earth element recovery method from precious metal smelting slag |
| CN105695738B (en) * | 2016-03-25 | 2017-11-28 | 武汉科技大学 | A kind of method for removing iron of Rock coal containing alum leachate |
| CN107502740B (en) * | 2017-06-26 | 2019-12-13 | 四川大学 | method for recovering iron resource from pyrolusite leaching slag |
| CN108531729A (en) * | 2018-04-18 | 2018-09-14 | 武汉科技大学 | A kind of vanadium iron separation method containing vanadium solution |
| JP7044082B2 (en) * | 2019-02-05 | 2022-03-30 | 信越化学工業株式会社 | Method for producing acidic slurry and method for recovering rare earth elements |
| CN110358923B (en) * | 2019-08-15 | 2021-01-01 | 昆明理工大学 | Method for extracting indium and recycling zinc oxide smoke dust by using zinc oxide smoke dust |
| CN110607537B (en) * | 2019-09-26 | 2021-02-26 | 江西理工大学 | Method for synchronously and efficiently extracting rare earth and iron from high-value recycled neodymium iron boron waste |
| CN111041200B (en) * | 2019-11-18 | 2021-02-19 | 北京科技大学 | Method for leaching vanadium, titanium and chromium from vanadium, titanium and chromium raw materials by organic acid through hydrothermal method |
| CN113787085A (en) * | 2021-10-14 | 2021-12-14 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
-
2021
- 2021-10-14 CN CN202111198498.3A patent/CN113787085A/en active Pending
-
2022
- 2022-05-12 WO PCT/CN2022/092438 patent/WO2023060889A1/en unknown
- 2022-07-15 CN CN202210836286.1A patent/CN115532770A/en active Pending
- 2022-07-15 CN CN202210835876.2A patent/CN115463935B/en active Active
-
2023
- 2023-02-23 ZA ZA2023/02411A patent/ZA202302411B/en unknown
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08152124A (en) * | 1994-11-28 | 1996-06-11 | Ishikawajima Harima Heavy Ind Co Ltd | Decomposition method of molten salt in incinerated ash melting furnace |
| JPH108150A (en) * | 1996-06-21 | 1998-01-13 | Tama Kagaku Kogyo Kk | Combustion treatment of waste material coated and deposited with metallic foil of secondary battery |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
| WO2014056143A1 (en) * | 2012-10-09 | 2014-04-17 | 上海交通大学 | Lithium iron phosphate material and preparation thereof |
| WO2015006796A1 (en) * | 2013-07-17 | 2015-01-22 | Technological Resources Pty. Limited | Treatment of minerals |
| CN103746115A (en) * | 2013-12-13 | 2014-04-23 | 灵宝金源矿业股份有限公司 | Method for preparing cell-grade lithium iron phosphate from pyrite slag |
| CN105129761A (en) * | 2015-08-31 | 2015-12-09 | 无锡市嘉邦电力管道厂 | Method for preparing ferrous phosphate positive pole material |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
| CN110112481A (en) * | 2019-04-23 | 2019-08-09 | 北京科技大学 | Waste lithium iron phosphate battery recycles the method for preparing lithium iron phosphate positive material |
| CN110306044A (en) * | 2019-07-18 | 2019-10-08 | 北京科技大学 | A kind of method of the hydro-thermal oxalic acid complexation leaching vanadium iron spinelle containing vanadium in vanadium mineral |
| CN110256235A (en) * | 2019-07-26 | 2019-09-20 | 攀枝花学院 | A method of ferrous oxalate is prepared using vanadium slag |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023060889A1 (en) | 2023-04-20 |
| CN115463935A (en) | 2022-12-13 |
| ZA202302411B (en) | 2023-05-31 |
| CN115532770A (en) | 2022-12-30 |
| CN113787085A (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115463935B (en) | Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry | |
| CN101818251B (en) | Method for recovering cobalt and lithium from waste lithium ion batteries | |
| CN109095481B (en) | Comprehensive recovery method of waste lithium iron phosphate powder | |
| CN101555030A (en) | Method for recovering and recycling waste lithium ion battery cathode material | |
| CN110343864A (en) | The method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material | |
| CN103746115A (en) | Method for preparing cell-grade lithium iron phosphate from pyrite slag | |
| CN114606386B (en) | Process for recovering cobalt and lithium by grinding and leaching waste lithium battery | |
| CN113292057B (en) | Recovery method of waste lithium iron phosphate battery | |
| CN109750155A (en) | A method of the Call Provision from waste lithium ion cell anode material | |
| EP4324949A1 (en) | Method for recovering valuable metals from spent lithium-ion batteries | |
| CN102820468A (en) | Preparation process of cobaltosic oxide for continuous production of batteries | |
| CN108328659A (en) | A kind of method that integrated treatment utilizes high magnesium ferronickel slag | |
| CN103911514A (en) | Waste hard alloy grinding material recovery treatment method | |
| CN112095000A (en) | Method for recovering cobalt and lithium metals from waste lithium cobalt oxide batteries | |
| Wang et al. | Oxygen-free calcination for enhanced leaching of valuable metals from spent lithium-ion batteries without a reductant | |
| CN101170204A (en) | Vacuum carbon heat recycling technology for thrown lithium ion battery | |
| Zheng et al. | Gas exchange-driven carbothermal reduction for simultaneous lithium extraction from anode and cathode scraps | |
| CN113979655A (en) | Modified steel slag based on steel dust mud and red mud, and preparation method and application thereof | |
| CN113184821B (en) | Method for preparing ferric phosphate from iron-containing slag | |
| CN105110300B (en) | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur | |
| CN103952537A (en) | Method for extracting high-quality iron powder and borax from paigeite | |
| Hu et al. | High-efficiency selective leaching of valuable metals from spent lithium-ion batteries: Effects of Na2S2O8 on the leaching of metals | |
| CN111646445B (en) | Green recovery processing method for anode of waste lithium iron phosphate battery | |
| CN108330276A (en) | Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application | |
| CN104059714A (en) | Method for preparing Fe2O3/Al2O3 oxygen carrier by taking ferrous metallurgy dust mud as main raw materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |