CN115463935A - Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid wastes in metallurgical industry - Google Patents
Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid wastes in metallurgical industry Download PDFInfo
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Abstract
The invention discloses a method for preparing lithium iron phosphate as a lithium battery anode material by using iron-rich solid wastes in the metallurgical industry, which takes a large amount of iron-rich solid wastes/dangerous wastes of iron and steel enterprises, electric furnace dust removal ash, iron oxide red or iron scale as raw materials, adopts oxalic acid as a leaching agent and iron powder as a reducing agent, and prepares high-purity ferrous oxalate by hydrothermal complex leaching and hydrothermal reduction complex precipitation; and then, the lithium iron phosphate serving as the lithium battery anode material with high purity and good physical and chemical properties is synthesized by taking ferrous oxalate as a raw material through a solid-phase reaction, and finally, the purposes of recycling and high-valued, green and low-cost utilization of a great amount of iron-rich solid waste/hazardous waste in metallurgy are achieved. The technical scheme provided by the method has the advantages of short process flow, simple equipment, low reaction temperature and higher product added value, and the first reversible specific capacity of the prepared lithium battery anode material lithium iron phosphate is 146.43 mAh.g ‑1 After 20 times of circulation, the capacity retention rate is still 100%, and the product has a wide marketThe field foreground.
Description
Technical Field
The invention belongs to the technical field of high-valued utilization of iron-rich solid wastes in metallurgical industry, and particularly relates to a method for preparing a high-added-value lithium battery anode material lithium iron phosphate by green extraction of iron-containing solid wastes of iron and steel enterprises, which is particularly suitable for iron in iron-rich solid waste resources, wherein iron mainly comprises Fe 3+ The content of iron is more than or equal to 40 percent, and impurity elements of CaO, mgO and SiO exist 2 、Al 2 O 3 And organic matters and other impurities with the content not higher than 15 percent.
Background
As non-renewable resources such as petroleum, coal, natural gas, etc. are gradually consumed, development and utilization of new energy resources, such as nuclear energy, solar energy, electric energy, etc., are gradually becoming research hotspots of researchers and key development directions of industry layout. By taking a cheap and convenient electrochemical energy storage device as an example, the lithium ion battery has the characteristics of long cycle life, high use safety and environment friendliness, and is very fast in application and development. In 2020, the yield of lithium batteries in China reaches nearly 500 hundred million, and the lithium batteries are increased by more than 150 percent on a same scale; the output of the power battery reaches 217GWH, which is the largest consumer end, and is expected to reach over 1000GWH in 2025. The method not only provides a huge market application prospect for the development of lithium battery production technology, but also provides higher requirements and challenges for the improvement of lithium battery material performance and the optimal control of cost.
Taking the lithium ion battery itself as an example, the positive electrode material and the negative electrode material often occupy a larger proportion. Therefore, the properties of the lithium battery cathode material directly affect the performance of the lithium ion battery, and the cost directly determines the cost of the whole battery. In a batch of lithium battery anode materials emerging in recent years, 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 an energy storage material with the best comprehensive performance and the best application prospect at present. With the vigorous 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 expanded, and the lithium iron phosphate material has a very wide popularization and application prospect. The method has the advantages that the applicable range of the iron source in the lithium iron phosphate material is expanded, the preparation process of the lithium iron phosphate is optimized, and the key points for solving the market problem and the cost problem are achieved. Most solid waste resources generated by metallurgical enterprises have rich Fe resources, and if the Fe resources can be used as raw materials for synthesizing lithium iron phosphate, the method can solve the urgent solid waste treatment problem for iron and steel enterprises, can greatly reduce the production cost of the lithium iron phosphate from the source, and has very obvious social benefit and economic benefit. Taking the dust removed from the electric furnace as an example, the dust removed from the electric furnace contains a large amount of Fe and Zn resources and iron content (Fe 2 O 3 Calculated) and Zn content (calculated by ZnO) can respectively reach more than 40 percent and 10 percent, and is a typical large iron-rich hazardous waste. However, due to the restriction of the technical level and the increasingly strict environmental policy, the main treatment method at present is mainly to recycle the iron-containing zinc in a rotary hearth furnace or a rotary kiln, which not only causes the serious waste of Fe and Zn resources, but also brings about a series of serious environmental problems. Iron oxide red is the treatment of waste pickling liquid and waste slag of iron and steel enterprisesThe resource utilization products generated in standing are mainly used for preparing magnetic ferrite or pigment for the utilization of iron oxide red at present. However, the method has the defects of low added value of products, complex process flow, high 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, said method firstly utilizes excess sodium hydroxide to convert iron element in the iron-containing waste into iron hydroxide or ferrous hydroxide, then under the condition of closed environment and 400-800 deg.C, utilizes two-step drying process to prepare gamma-Fe 2 O 3 . However, the alkali consumption is high, the process flow is long, the product purity is low, and the initiative of the enterprise for carrying out technical improvement is not positive. The patent "a method for producing high-purity iron powder by using iron slag" (CN 201711066037.4) provides a method for preparing high-purity iron powder by using converter steel slag. Firstly, adding iron slag into a soaking solution composed of sodium hydroxide, sodium methallyl sulfonate and deionized water for removing impurities, placing filter residues into an electrolytic cell for electrolysis to prepare metal iron powder, then placing the iron powder separated out from a cathode into an ethylene diamine tetraacetic acid solution for cleaning to remove impurity ions adsorbed on the surface, and finally obtaining the iron powder with the purity of more than 95%. However, the method has long process flow, large medicament consumption and large generation amount of waste residues and waste liquid, 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 high-value utilization of iron-rich solid waste, namely preparation of lithium iron phosphate as a lithium battery cathode material, aiming at the cost problem and the environmental problem faced by the existing iron and steel enterprise iron-rich solid waste resource utilization technology. The method takes a large amount of iron-rich waste in the metallurgical industry as an initial raw material (such as iron oxide red, electric furnace dust removal ash, blast furnace ash and the like), selects oxalic acid as a leaching agent and iron powder as a reducing agent, and converts rich iron resources into an important raw material for synthesizing lithium iron phosphate, namely ferrous oxalate; and then, taking the prepared ferrous oxalate as an iron source for synthesizing lithium iron phosphate, taking ammonium dihydrogen phosphate as a phosphorus source, and taking lithium hydroxide or lithium carbonate as a lithium source, and preparing the lithium iron phosphate serving as the lithium battery anode material with high added value by adopting a solid-phase synthesis method. The resource and high-value utilization method for the bulk iron-rich solid waste in the metallurgical industry provided by the invention not only meets the treatment requirements of reduction, resource and harmlessness of the solid waste, realizes the purposes of source reduction of the solid waste and overall process control of pollutants, and the generated high-value-added product can bring actual profits to enterprises and 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 product added value, complex process flow, large production amount of waste residues and waste liquid and high production cost in the traditional process for treating iron-rich solid wastes in the metallurgical industry, and provides a method for preparing lithium battery anode material lithium iron phosphate by using the iron-rich solid wastes in the metallurgical industry, which has the advantages of short process flow, simple equipment, low reaction temperature, milder reaction conditions, higher product added value and less lithium source usage.
In order to achieve the purpose, the invention takes iron-containing solid wastes generated in actual production activities of iron and steel enterprises as raw materials, selects oxalic acid as a leaching agent and iron powder as a reducing agent, converts rich iron in the iron into high-purity ferrous oxalate through hydrothermal complex leaching and hydrothermal reduction complex precipitation, and takes the obtained ferrous oxalate as a main raw material to prepare the lithium ion battery cathode material lithium iron phosphate with good physical and chemical properties. The method for preparing the lithium iron phosphate as the positive electrode material of the lithium battery by using the iron-rich solid wastes in the metallurgical industry is implemented by adopting the following steps:
1) Preparing raw materials: taking iron-rich dangerous/solid wastes of iron and steel enterprises as raw materials, and carrying out crushing and grinding operation treatment to obtain fine iron-rich materials with the-0.074 mm grade content of more than or equal to 80.0%, preferably with the-0.074 mm grade content of more than or equal to 90.0%.
If the water content of the raw material is high, drying treatment is carried out before grinding. After obtaining fine iron-rich materials with proper particle size, the occurrence state and content of Fe need to be clarified so as to determine the specific mode for comprehensively utilizing the Fe.
The iron-rich hazardous/solid waste of the iron and steel enterprises is generally solid waste such as electric furnace dust removal ash, iron oxide red, iron scale (steel rolling iron scale) and the like.
2) Performing hydrothermal complex leaching to extract iron: adding the fine iron-rich material obtained in the step 1) and an oxalic acid solution with a designed concentration according to a calculated liquid-solid ratio, fully and uniformly mixing, putting the mixture into constant-temperature reaction equipment, and regulating and controlling the reaction temperature and the reaction time to enable iron oxide in the fine iron-rich material to perform a hydrothermal complexation reaction to generate Fe (C) which is easily dissolved in water and an acid solution 2 O 4 ) 3 3- And free in solution; and after the hydrothermal complexation reaction is finished, carrying out solid-liquid separation on the reaction product, and filtering, washing and purifying for multiple times to obtain the iron-rich complex ion leaching solution I.
The plurality of times means 3 times or more. According to different raw materials in the step 1), the amount and components of the residue after solid-liquid separation are different. If the iron oxide red or the iron scale is adopted as the raw material in the step 1), the residual slag amount is very small, and the residual slag can be directly mixed into the smelting furnace burden as an ingredient; if the electric furnace dust removal ash is adopted as the raw material in the step 1), a large amount of residual slag is generated, and the components in the residual slag comprise CaO, mgO and SiO 2 、Al 2 O 3 Mainly used as the ingredients of ceramic particles and building bricks; if the lead and the zinc are contained, the lead and the zinc are treated by a curing and stabilizing method to prepare baking-free bricks or sintered bricks which meet the MU15 strength grade requirement of solid concrete bricks (GB/T21144-2007) and have leaching toxicity lower than the limit requirement of hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007), or after valuable metal elements such as lead, zinc and the like are extracted, products such as ceramsite, baking-free bricks and the like are prepared, and finally, the full-quantization and high-value comprehensive utilization of the iron-rich solid waste in the metallurgical industry is 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 ratio and the reaction time, and separating out ferrous oxalate crystals from the solution at normal temperature and normal pressure; after solid-liquid separation, the separated ferrous oxalate crystal is dried in vacuum to obtain high-purity ferrous oxalate powder with the purity of more than or equal to 98.0 percent.
4) Synthesizing lithium iron phosphate through solid-phase reaction: 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 reductive roasting atmosphere, heat preservation is carried out at two different roasting temperatures of 350-500 ℃ and 650-900 ℃ in sequence, the heat preservation time is 10-20 h and 20-32 h in sequence, and finally a lithium iron phosphate product which meets the performance requirement of the lithium battery anode material and has excellent electrochemical performance is obtained.
Further, in the step 1), fe in the iron-rich danger/solid waste of the steel enterprise is Fe 2 O 3 Preferably, fe is 2 O 3 The iron in the raw materials accounts for more than 30 percent of the total mass of the raw materials; preferably, fe is present in the form of Fe 3+ 、Fe 2+ With Fe 0 Wherein Fe is 3+ The content is preferably more than 70% of the total amount of Fe.
Further, the liquid-solid ratio (ml/g) of the oxalic acid to the fine-grained iron-rich material in the step 2) is favorably in the range of (10-40) to 1, preferably (15-20) to 1; the mass concentration of the oxalic acid solution is preferably 10 to 50 percent, and preferably 20 to 25 percent; 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 the oxalic acid added in the step 3) to the Fe in the iron-rich complex ion leaching solution I is (0.5-2.5) to 1, preferably (1.0-2.0) to 1; the mass ratio of the reduced iron powder to Fe in the iron-rich complex ion leaching solution I is (3-4) to 1, and the reaction temperature is 60-90 ℃, preferably 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 10.13-30.39 kPa, preferably 10.13-20.26 kPa; 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 ammonium dihydrogen phosphate is (2.0-2.5): 1: (2.0 to 2.5) is preferable; a two-step solid-phase synthesis method is adopted, and under the reductive roasting atmosphere, the synthesis of lithium iron phosphate is divided into two stages: in the first stage, the temperature is preferably kept for 12 to 15 hours at the roasting temperature of 400 to 450 ℃; on the basis of finishing the reaction of the first stage, the temperature is continuously raised to 700-900 ℃ to enter the second stage, and the temperature is preferably kept 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 iron phosphate as the lithium battery anode material by using the iron-rich solid wastes in the metallurgical industry has the following advantages:
(1) The invention provides a method for preparing a lithium ion battery anode material lithium iron phosphate with high added value by treating bulk iron-rich solid wastes in the metallurgical industry through a wet method, and finally achieving the recycling and high-value utilization of the bulk iron-rich solid wastes in metallurgy, belonging to the original innovative technology. The process has the advantages that the defects of high roasting temperature and large emission of the traditional treatment process are overcome, the iron-containing solid wastes are used as raw materials, the pollution to the ecological environment is eliminated, and the raw material cost of the lithium battery anode material lithium iron phosphate is reduced. The whole technical process is considered, 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 serving as a lithium battery anode material by using iron-rich solid wastes in the metallurgical industry. Compared with the conventional technology, the reaction mother liquor is returned to the pre-reaction process for cyclic utilization, the by-product is not needed to be neutralized, a large amount of alkali liquor needed by neutralization reaction is saved, the discharge of waste water is greatly reduced, and the environmental protection treatment cost can be reduced by more than 60 percent; the process route is simple and controllable, the yield can reach more than 90 percent, and the method is suitable for industrial scale production;
(3) The invention provides a method for recycling and high-valued utilizing bulk iron-rich solid wastes in the metallurgical industry. The characteristics of the lithium iron phosphate material are combined, iron-containing solid waste in the metallurgical industry is used as a raw material, and different reaction conditions are selected to prepare ferrous oxalate powder with the particle size of 0.5-10 mu m, so that the particle size is completely controllable; the product purity is more than 98.5 percent and can reach 99.5 percent at most, the product quality requirement of downstream battery production enterprises is met, the added value of the product is higher, and the product has higher competitiveness in the market;
(4) The invention provides a method for finally preparing a high-added-value product lithium iron phosphate by using a large amount of iron-rich solids in the metallurgical industry as a raw material and performing resource and high-value utilization on the raw material. In terms of the overall production process flow of the lithium iron phosphate, the preparation cost can be reduced by 60-70%, the technical and economic values are high, and the method has an industrial prospect compared with the traditional process; 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 battery anode material lithium iron phosphate prepared by the method has the first reversible specific capacity of 146.43 mAh.g -1 After circulating for 20 times, the solution still maintains 146.63mAh g -1 The capacity retention rate is 100%, which shows that the material has excellent cycling stability.
(6) 2025 button cells were assembled for electrochemical testing: the three-time charge and discharge curves are basically superposed, thereby showing that LiFePO 4 Has good cycle stability in the charging and discharging processes.
Drawings
FIG. 1 is a process flow diagram of the principle of the method for preparing lithium iron phosphate as the positive electrode material of a lithium battery by using iron-rich solid wastes in the metallurgical industry according to the present invention;
FIG. 2 is a diagram of XRD diffraction pattern of ferrous oxalate powder prepared by using iron-containing solid waste iron oxide red of iron and steel enterprises as raw material, and Cu-Kalpha target radiation is adopted, the diffraction angle 2 theta is 10-90 ℃, and the X-ray wavelength lambda =0.15416nm;
FIG. 3 is a XRD diffraction pattern of lithium iron phosphate powder prepared by using iron-containing solid waste iron oxide red of iron and steel enterprises as an initial raw material according to the method of the invention, and Cu-Kalpha target radiation is adopted, the diffraction angle 2 theta is 10-90 ℃, and the X-ray wavelength lambda =0.15416nm;
FIG. 4 is an XRD diffraction pattern of ferrous oxalate powder prepared by using iron-containing hazardous waste electric furnace dust of iron and steel enterprises as a raw material according to the method of the invention, and Cu-Ka target radiation is adopted, the diffraction angle 2 theta is 10-90 ℃, and the X-ray wavelength lambda =0.15416nm;
FIG. 5 is an XRD diffraction pattern of lithium iron phosphate powder 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, and Cu-Ka target radiation is adopted, the diffraction angle 2 theta is 10-90 ℃, and the X-ray wavelength lambda =0.15416nm;
FIG. 6 is a graph showing the previous three charge and discharge curves of a lithium iron phosphate material prepared under a constant current charge and discharge test at a current density of 0.1C;
FIG. 7 shows 2.5 to 4.2V (vs. Li/Li) + ) Within the potential range of (1) and under the current density of 0.1C, a cycle performance curve diagram of the lithium iron phosphate material prepared by experiments is shown.
Detailed Description
For describing the present invention, the method for preparing lithium iron phosphate as the positive electrode material of the lithium battery from iron-rich solid wastes in the metallurgical industry according to the present invention will be described in further detail with reference to the accompanying drawings and examples.
As shown in fig. 1, the principle process flow chart of the method for preparing lithium iron phosphate as the positive electrode material of the lithium battery by using iron-rich solid wastes in the metallurgical industry is shown, and the method for preparing lithium iron phosphate as the positive electrode material of the lithium battery by using iron-rich solid wastes in the metallurgical industry is implemented by adopting the following steps:
1) Preparing raw materials: taking iron-rich dangerous/solid waste-electric furnace dust removal ash and iron oxide red or iron scale of iron and steel enterprises as raw materials, and drying, crushing and grinding the raw materials to obtain a fine iron-rich material with the grain size of-0.074 mm and the content of more than or equal to 90.0%; the iron element in the selected raw material is Fe 3+ 、Fe 2+ With Fe 0 And with Fe 2 O 3 Mainly of Fe, wherein 2 O 3 The iron in the raw materials accounts for more than 30 percent of the total mass of the raw materials, and Fe 3+ The content of Fe is preferably more than 70% of the total amount of Fe.
2) Performing hydrothermal complex leaching to extract iron: adding the fine 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 iron-rich material (15-20) to 1, fully and uniformly mixing, and then placing the mixture into constant-temperature reaction equipmentThe reaction temperature is 70-85 ℃, the reaction time is 1.5-2.5 h, so that the iron oxide in the fine iron-rich material undergoes a hydrothermal complexation reaction to generate Fe (C) which is easily dissolved in water and acid liquor 2 O 4 ) 3 3- And free in solution; and after the hydrothermal complexing reaction is finished, carrying out solid-liquid separation on a reaction product, and filtering, washing and purifying for multiple times to obtain the iron-rich complex ion leaching solution I.
3) Preparing ferrous oxalate by performing hydrothermal reduction and 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 ratio 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; after solid-liquid separation, the separated ferrous oxalate crystal is subjected to vacuum drying treatment, wherein the vacuum drying temperature is 60-70 ℃, the vacuum degree is 10.13-20.26 kPa, and the drying time is 8-12 h, so that high-purity ferrous oxalate powder with the purity of more than or equal to 98.5% is obtained.
4) Synthesizing lithium iron phosphate through solid-phase reaction: 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 reductive roasting atmosphere, heat preservation is carried out at different roasting temperatures of 400-450 ℃ and 750-800 ℃ in sequence, the heat preservation time is 12-15 h and 24-28 h in sequence, and finally a lithium iron phosphate product meeting the performance requirements of the lithium battery anode material is obtained. In the step, 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: (2.0-2.5).
The invention will be described in detail with reference to specific examples:
example 1:
(1) Weighing 1g of iron oxide red which is typical bulk solid waste of a martensite steel company, drying, crushing, grinding, and then sieving with a 200-mesh sieve to confirm that the granularity of more than 90 percent 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: the leaching temperature is 85 ℃, the reaction time is 2h, and the stirring speed is set to be 400r/min; after the hydrothermal complexation reaction is finished, carrying out solid-liquid separation on a 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, the Fe concentration in the leachate I was found to be 2572mg/L by ICP-AES analysis.
(3) The leaching solution I in the above arrangement is used as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 1.08g of oxalic acid and 2.02g of reduced iron powder, leaching at 85 ℃, reacting for 2h, and stirring at 400r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and carrying out vacuum drying on the solid obtained by the filtration reaction for 12 hours at the temperature 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 seen from fig. 2, the Cu — K α target radiation used had a diffraction angle 2 θ of 10 to 90 ℃ and an X-ray wavelength λ =0.15416nm. As can be seen from fig. 2: compared with a ferrous oxalate standard card, the ferrous oxalate powder prepared by utilizing the iron oxide red has good crystallization property, high strength and no impurity peak.
(4) The iron oxalate obtained in the previous step is used as a raw material, a solid-phase reaction method is adopted, and the lithium iron phosphate is prepared by a two-step method, wherein 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, and alcohol is used as a medium to be fully ground to prepare a precursor; under the reductive roasting condition, firstly, preserving the heat for 12 hours at the temperature of 400 ℃; after the heat preservation is finished, immediately heating, and continuously preserving heat for 24 hours under the experimental condition of 750 ℃; after the reaction is finished, cooling the system, taking out the 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 — K α target radiation used had a diffraction angle 2 θ of 10 to 90 ℃ and an X-ray wavelength λ =0.15416nm. As can be seen from fig. 3: compared with a standard lithium iron phosphate card, the lithium iron phosphate powder prepared by using the iron oxide red has good crystallization property 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) Weighing 1g of electric furnace dedusting ash which is typical bulk iron-containing hazardous waste of a Martin company, drying, crushing, grinding, and then screening with a 200-mesh screen to confirm that the granularity of more than 90 percent 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: the leaching temperature is 80 ℃, the reaction time is 2.5h, and the stirring speed is set to be 400r/min; after the hydrothermal complexation reaction is finished, carrying out solid-liquid separation on a 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, the concentration of Fe in the leachate I was 1575mg/L as determined by ICP-AES analysis.
(3) The leaching solution I in the above arrangement is used as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 0.64g of oxalic acid and 1.18g of reduced iron powder, leaching at 85 ℃, reacting for 2h, and stirring at 400r/min. After the reaction is finished, cooling the solution to room temperature for solid-liquid separation, and drying the solid obtained by the filtration reaction in vacuum for 12 hours at 65 ℃ and under 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 4. As can be seen from fig. 4, the Cu — K α target radiation used had a diffraction angle 2 θ of 10 to 90 ℃ and an X-ray wavelength λ =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 removal ash has good crystallization property, high peak strength and no impurity peak.
(4) The iron phosphate lithium is prepared from the ferrous oxalate obtained in the previous step as a raw material by a solid-phase reaction method through a two-step method, and the specific experimental conditions are as follows: weighing 1.2g of ferrous oxalate, 0.25g of lithium carbonate and 0.77g of ammonium dihydrogen phosphate respectively, and fully grinding by using alcohol as a medium to prepare a precursor; under the reductive roasting condition, firstly, preserving heat for 12 hours at 450 ℃, immediately heating after heat preservation is finished, and preserving heat for 24 hours under the experimental condition of 750 ℃; and (3) after the reaction is finished, cooling the system, taking out the sample after the furnace body is cooled, wherein the XRD diffraction pattern of the reaction product is shown in figure 5. As can be seen from fig. 5, the Cu — K α target radiation used has a diffraction angle 2 θ of 10 to 90 ℃, and an X-ray wavelength λ =0.15416nm. As can be seen from fig. 5: compared with a standard lithium iron phosphate card, the lithium iron phosphate powder prepared by using the electric furnace dust removal ash has good crystallization property and high peak strength, and does not contain any impurity peak.
(5) To study LiFePO 4 Electrochemical performance of the LiFePO obtained in the step (4) 4 The prepared pole piece is an active electrode, the metal lithium is a counter electrode, and the 2025 button cell is assembled for electrochemical test: for LiFePO at a current density of 0.1C in the potential range of 2.5-4.2V (vs. Li/Li +) 4 And carrying out constant current charge and discharge test. Fig. 6 is a charging and discharging curve diagram of the first three times when constant current charging and discharging tests are performed on the prepared lithium iron phosphate material at a current density of 0.1C. As seen in FIG. 6, liFePO 4 The first charge-discharge specific capacities of the positive electrode material and the negative electrode material are 142.17mAh g-1 and 146.47mAh g respectively -1 The first coulombic efficiency of the material is 103.0%; in addition, the second and third charge-discharge curves substantially coincide, indicating LiFePO 4 Has good cycle stability in the charging and discharging process.
(6) In order to verify the cycling stability of the experimentally prepared lithium iron phosphate material, experiments subsequently determined that LiFePO was prepared within a potential range of 2.5-4.2V (vs. Li/Li +) 4 The cycling performance curve at 0.1C current density is shown in fig. 7: as seen in FIG. 6, liFePO 4 The first reversible specific capacity is 146.43 mAh.g -1 After circulating for 20 times, the solution still maintains 146.63mAh g -1 The capacity retention rate is 100%, which shows that the material has excellent cycling stability.
Claims (10)
1. A method for preparing lithium iron phosphate as a lithium battery anode material by using iron-rich solid wastes in the metallurgical industry is characterized by comprising the following steps:
1) Preparing raw materials: taking iron-rich dangerous/solid wastes of iron and steel enterprises as raw materials, and carrying out crushing and grinding operation treatment to obtain fine iron-rich materials with the grain size fraction of-0.074 mm and the content of more than or equal to 80.0%;
2) Performing hydrothermal complex leaching to extract iron: adding the fine 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, putting the mixture into constant-temperature reaction equipment, regulating and controlling the reaction temperature and the reaction time to enable iron oxide in the fine iron-rich material to perform hydrothermal complexation reaction to generate Fe (C) which is easily dissolved in water and acid solution 2 O 4 ) 3 3- And free in solution; after the hydrothermal complexation reaction is finished, carrying out solid-liquid separation on a reaction product, and filtering, washing and purifying for multiple times to obtain an iron-rich complex ion leaching solution I;
3) Preparing ferrous oxalate by performing hydrothermal reduction and 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 ratio and the reaction time, and separating out ferrous oxalate crystals from the solution at normal temperature and normal pressure; 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) Synthesizing lithium iron phosphate through solid-phase reaction: 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 reductive roasting atmosphere, heat preservation is carried out at two different roasting temperatures of 350-500 ℃ and 650-900 ℃ in sequence, the heat preservation time is 10-20 h and 20-32 h in sequence, and finally a lithium iron phosphate product meeting the performance requirements of the lithium battery anode material is obtained.
2. The method for preparing lithium iron phosphate as the cathode material of the lithium battery from the iron-rich solid waste in the metallurgical industry as claimed in claim 1, wherein the method is characterized in thatThe method comprises the following steps: fe in the iron-rich danger/solid waste of the steel enterprise in the step 1) is Fe 2 O 3 Mainly of Fe, wherein 2 O 3 The iron in the raw materials accounts for more than 30 percent of the total mass of the raw materials.
3. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery 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 In which Fe 3+ The content accounts for more than 70 percent of the total amount of Fe element.
4. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery from 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 the oxalic acid to the fine-grain iron-rich material in the step 2) is (10-40) to 1, the mass concentration of the oxalic acid solution is 10-50%, the reaction temperature is 50-95 ℃, and the reaction time is 1-5 hours.
5. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery 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 the oxalic acid to the fine-grain iron-rich material in the step 2) is (15-20) to 1, the mass concentration of the 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 lithium iron phosphate as the positive electrode material of the lithium battery from 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 the oxalic acid added in the step 3) to the Fe in the iron-rich complex ion leaching solution I is (0.5-2.5) to 1, the mass ratio of the reduced iron powder to the Fe in the iron-rich complex ion leaching solution I is (3-4) to 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 lithium iron phosphate as the positive electrode material of the lithium battery from 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 the oxalic acid added in the step 3) 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, and the reaction temperature is 75-85 ℃.
8. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery 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 h.
9. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery 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 h.
10. The method for preparing lithium iron phosphate as the positive electrode material of the lithium battery from 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: (2.0-2.5); the first stage is at 400-450 deg.c for 12-15 hr and the second stage is at 750-800 deg.c for 24-28 hr.
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| 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 |
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| 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 (14)
| 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 |
| US20090035204A1 (en) * | 2007-07-31 | 2009-02-05 | Byd Company Limited | Methods for Synthesizing Lithium Iron Phosphate as a Material for the Cathode of Lithium Batteries |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
| US20110089045A1 (en) * | 2008-04-11 | 2011-04-21 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| 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 |
| US20140239235A1 (en) * | 2012-07-20 | 2014-08-28 | Shenzhen Dynanonic Co., Ltd. | Auto-thermal evaporative liquid-phase synthesis method for cathode material for battery |
| 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 (12)
| 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 |
| 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 |
| 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 (14)
| 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 |
| US20090035204A1 (en) * | 2007-07-31 | 2009-02-05 | Byd Company Limited | Methods for Synthesizing Lithium Iron Phosphate as a Material for the Cathode of Lithium Batteries |
| US20110089045A1 (en) * | 2008-04-11 | 2011-04-21 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
| US20140239235A1 (en) * | 2012-07-20 | 2014-08-28 | Shenzhen Dynanonic Co., Ltd. | Auto-thermal evaporative liquid-phase synthesis method for cathode material for battery |
| 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 |
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