CN115353129A - Method for recycling anode material of waste lithium iron phosphate battery - Google Patents
Method for recycling anode material of waste lithium iron phosphate battery Download PDFInfo
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- CN115353129A CN115353129A CN202211187637.7A CN202211187637A CN115353129A CN 115353129 A CN115353129 A CN 115353129A CN 202211187637 A CN202211187637 A CN 202211187637A CN 115353129 A CN115353129 A CN 115353129A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The application provides a method for recovering a positive electrode material of a waste lithium iron phosphate battery, which comprises the steps of mixing lithium carbonate, phosphorus oxide and an alkaline solution for reaction, and carrying out solid-liquid separation to obtain lithium carbonate and a solution containing phosphate radicals. The application provides a recovery method of old and useless lithium iron phosphate battery cathode material, through making alkaline solution and lithium carbonate and phosphorus oxide mixing reaction, the phosphorus oxide is dissolved in aquatic and is generated phosphoric acid, phosphoric acid and alkaline solution mixing reaction produce the solution that contains the phosphate radical, pass through solid-liquid separation and will be difficult to be dissolved in lithium carbonate of water and the solution separation that contains the phosphate radical, with the phosphorus impurity that the in-process that retrieves lithium carbonate from old and useless lithium iron phosphate battery cathode material produced, thereby improve the purity of the lithium carbonate of retrieving from old and useless lithium iron phosphate battery cathode material. And the recovered solution containing phosphate can be used for preparing lithium iron phosphate again. Therefore, the recovery method provided by the application can effectively improve the material recovery rate of the anode material of the waste lithium iron phosphate battery.
Description
Technical Field
The application belongs to the technical field of waste battery recovery, and particularly relates to a method for recovering a positive electrode material of a waste lithium iron phosphate battery.
Background
As the demand of lithium batteries has been increasing, the number of waste lithium batteries has also been increasing. Specifically, the lithium iron phosphate battery is a commonly used lithium battery, so the number of waste lithium iron phosphate batteries is also increasing continuously. The waste lithium iron phosphate battery positive electrode material contains a large amount of lithium elements and phosphorus elements, the lithium elements and the phosphorus elements are used as important components of the lithium iron phosphate battery positive electrode material, the recycling can increase economic benefits, protect the environment and reduce the probability that the waste lithium iron phosphate battery enters the environment, and therefore the recycling of the waste lithium iron phosphate battery positive electrode material has important economic and environmental significance. At present, the carbothermic reduction technology is often applied to the recovery of the anode material of the waste lithium iron phosphate battery. However, during the recycling process, phosphorus oxide is generated from the waste lithium iron phosphate battery positive electrode material, so that phosphorus impurities, such as lithium phosphate, are doped in lithium carbonate, and the purity of lithium carbonate recycled from the waste lithium iron phosphate battery positive electrode material is reduced.
Disclosure of Invention
In view of this, the application provides a method for recovering a waste lithium iron phosphate battery positive electrode material, which includes:
providing lithium iron phosphate and a reducing agent;
heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide;
and mixing the lithium carbonate and the phosphorus oxide with an alkaline solution for reaction, and carrying out solid-liquid separation to obtain the lithium carbonate and a solution containing phosphate radicals.
The method for recovering the anode material of the waste lithium iron phosphate battery is simple, low in cost and high in operability. Specifically, after lithium iron phosphate and a reducing agent are heated and reacted in a reducing atmosphere or a protective atmosphere, phosphate radicals in the lithium iron phosphate are thermally decomposed into phosphorus oxide, and lithium elements in the lithium iron phosphate generate lithium carbonate. At this time, phosphorus oxide and lithium carbonate are mixed with each other, in other words, lithium carbonate is doped with phosphorus impurities. Then, lithium carbonate and phosphorus oxide are mixed with the alkaline solution. During the mixing process, lithium carbonate is difficult to dissolve in water, while phosphorus oxide is dissolved in water to generate phosphoric acid, and the phosphoric acid is mixed with an alkaline solution to react to generate a solution containing phosphate radicals. Subsequently, the lithium carbonate which is difficult to dissolve in water is separated from the solution containing phosphate radical through solid-liquid separation. In other words, the lithium carbonate is separated from the phosphorus impurities, and finally the lithium carbonate which does not contain the phosphorus impurities and has high purity is obtained, so that the lithium element in the anode material of the waste lithium iron phosphate battery is recycled.
And the recovered solution containing phosphate radicals can also be used for preparing lithium iron phosphate, so that the phosphorus element in the anode material of the waste lithium iron phosphate battery can be recycled.
The application provides a recovery method of old and useless lithium iron phosphate battery cathode material through making alkaline solution and lithium carbonate and phosphorus oxide mixing reaction to get rid of the phosphorus impurity that produces from the in-process of retrieving the lithium carbonate in old and useless lithium iron phosphate battery cathode material, thereby improve the purity of the lithium carbonate of retrieving from old and useless lithium iron phosphate battery cathode material. And the solution containing phosphate radicals is recovered and reused for preparing the lithium iron phosphate, so that the material recovery rate of the waste lithium iron phosphate battery anode material is effectively improved.
Wherein the step of heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain lithium carbonate and phosphorus oxide comprises:
heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain the lithium carbonate, the phosphorus oxide and the iron;
the step of mixing and reacting the lithium carbonate and the phosphorus oxide with an alkaline solution comprises the following steps:
and mixing the lithium carbonate, the phosphorus oxide and the iron with an alkaline solution, and carrying out solid-liquid separation to obtain the lithium carbonate, the iron and the solution containing phosphate radicals.
Wherein the alkaline solution satisfies at least one of the following conditions:
the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is (3-4): 1;
the pH value of the alkaline solution is 9-11.
When the alkaline solution contains ammonium ions, the solution containing phosphate radicals is an ammonium phosphate solution, and the ammonium phosphate solution is used for preparing the solution containing phosphate radicals, so that the solution containing phosphate radicals is used for preparing the lithium iron phosphate.
Wherein, in the process of mixing the lithium carbonate, the phosphorus oxide and the iron with the alkaline solution, the temperature T1 of the alkaline solution is 60-90 ℃, and the mixing time T1 is 0.5-1 h.
Wherein, after the steps of mixing the lithium carbonate, the phosphorus oxide, and the iron with an alkaline solution and performing solid-liquid separation to obtain the lithium carbonate, the iron, and the solution containing a phosphate group, the method comprises:
mixing and reacting the lithium carbonate, the iron and a carbonate-containing solution, and carrying out solid-liquid separation to obtain the iron and a lithium bicarbonate solution;
and evaporating and concentrating the lithium bicarbonate solution to obtain lithium carbonate with preset purity.
Wherein the preset purity P of the lithium carbonate is 99.3-99.8%.
Wherein, in the process of heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain the lithium carbonate and the phosphorus oxide, the heating temperature T2 is 710-850 ℃, and the heating time T2 is 3-12 h.
When the reducing agent contains carbon element, heating the lithium iron phosphate and the reducing agent containing carbon element in the reducing atmosphere or the protective atmosphere to obtain carbon dioxide, wherein the carbon dioxide is used for preparing the solution containing carbonate.
Wherein after the lithium carbonate and the iron are mixed and reacted with the carbonate-containing solution, the method comprises the following steps:
and introducing carbon dioxide into the carbonate-containing solution, wherein the flow rate F1 of the carbon dioxide is 5L/min-60L/min.
Drawings
In order to more clearly explain the technical solution in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.
Fig. 1 is a process flow chart of a method for recovering a positive electrode material of a waste lithium iron phosphate battery according to an embodiment of the present application.
Fig. 2 is a process flow diagram included in S200 and S300 in an embodiment of the present application.
Fig. 3 is a process flow chart of a method for recovering a positive electrode material of a waste lithium iron phosphate battery according to another embodiment of the present application.
Fig. 4 is a process flow diagram included in S310 in an embodiment of the present application.
Detailed Description
The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, various modifications and embellishments can be made without departing from the principle of the present application, and these modifications and embellishments are also regarded as the scope of the present application.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as encompassing the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
Before the technical solutions of the present application are introduced, the technical problems in the related art will be described in detail.
As the demand of lithium batteries has been increasing, the number of waste lithium batteries has also been increasing. The lithium iron phosphate battery is a lithium ion battery using lithium iron phosphate as a positive electrode material. The anode material of the lithium ion battery mainly comprises lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and the like. At present, the carbothermic reduction technology is often applied to the recovery of the anode material of the waste lithium iron phosphate battery. However, during the recycling process, phosphorus oxide, i.e., phosphorus pentoxide, is generated from the waste lithium iron phosphate battery positive electrode material, so that phosphorus impurities, e.g., lithium phosphate, are doped in lithium carbonate, and the purity of lithium carbonate recycled from the waste lithium iron phosphate battery positive electrode material is reduced.
Specifically, when phosphorus oxide is soaked in water, the phosphorus oxide reacts with water to produce phosphoric acid, lithium ions in the solution are caused to exist in the form of lithium phosphate, and lithium phosphate in the lithium carbonate-doped part obtained by filtration through evaporation concentration is caused to exist. Therefore, a process for converting lithium phosphate into lithium carbonate is required to be carried out later, and the complexity of the process is increased. In addition, in the process of recovering lithium carbonate, carbon dioxide waste gas is generated, the greenhouse effect is intensified, and the environment protection is not facilitated.
In view of this, in order to solve the above problems, the present application provides a method for recovering a positive electrode material of a waste lithium iron phosphate battery. Referring to fig. 1, fig. 1 is a process flow chart of a method for recovering a positive electrode material of a waste lithium iron phosphate battery according to an embodiment of the present application. The embodiment provides a method for recovering a positive electrode material of a waste lithium iron phosphate battery, which comprises S100, S200 and S300. The details of S100, S200, and S300 are as follows.
S100, providing lithium iron phosphate and a reducing agent.
In the embodiment, the provided lithium iron phosphate is derived from a positive electrode material of a waste lithium ion battery or other waste lithium iron phosphate materials.
Optionally, in an embodiment, after the step of providing lithium iron phosphate, the method includes: and crushing the lithium iron phosphate. Further optionally, a mechanical pulverizer is used to perform pulverization treatment on the lithium iron phosphate.
Through smashing lithium iron phosphate, can increase the reaction area of contact of lithium iron phosphate and reductant to accelerate the reaction time of lithium iron phosphate and reductant, promote the recovery efficiency of lithium carbonate.
In this embodiment, a reducing agent is also provided to react with lithium iron phosphate to obtain lithium carbonate. Alternatively, the reducing agent includes, but is not limited to, carbon powder, carbon monoxide, lithium, and the like.
Optionally, in an embodiment, the mass ratio of the reducing agent to the lithium iron phosphate is (0.05-0.1): 1.
optionally, the mass ratio of the reducing agent to the lithium iron phosphate is (0.06-0.09): 1. further optionally, the mass ratio of the reducing agent to the lithium iron phosphate is (0.07-0.08): 1.
the mass ratio of the reducing agent to the lithium iron phosphate is (0.05-0.1): 1, not only can the sufficient reaction of lithium iron phosphate and a reducing agent be ensured, so that phosphate radicals in the lithium iron phosphate are thermally decomposed into phosphorus oxide at high temperature, and lithium elements in the lithium iron phosphate generate lithium carbonate; and can save the cost and reduce the energy consumption. If the mass ratio of the reducing agent to the lithium iron phosphate is less than (0.05-0.1): 1, reducing agent is too little, so that sufficient reaction of lithium iron phosphate and the reducing agent cannot be ensured, and the recovery rate of lithium is reduced; if the mass ratio of the reducing agent to the lithium iron phosphate is more than (0.05-0.1): 1, the reducing agent is excessive, the cost is increased, and the energy consumption is increased. Among them, phosphorus oxide may also be referred to as phosphorus pentoxide.
And S200, heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide.
Uniformly stirring lithium iron phosphate and a reducing agent, and placing in a reducing atmosphere or a protective atmosphere, for example: heating in nitrogen, argon or carbon monoxide. And heating and reacting lithium iron phosphate with a reducing agent, wherein phosphate radicals in the lithium iron phosphate are thermally decomposed into phosphorus oxide at high temperature, and lithium elements in the lithium iron phosphate generate lithium carbonate. Since phosphorus oxide and lithium carbonate are both solid, phosphorus oxide and lithium carbonate are mixed with each other at this time and cannot be separated. In other words, lithium carbonate is doped with phosphorus impurities.
The phosphorus element in the lithium iron phosphate is present as a phosphate group.
Optionally, the reducing atmosphere includes, but is not limited to, carbon monoxide, and the like; the protective atmosphere includes, but is not limited to, nitrogen, argon, and the like.
Optionally, in the step of heating the lithium iron phosphate and the reducing agent to obtain lithium carbonate and phosphorus oxide, nitrogen is introduced at a flow rate F2 of 90L/min to 110L/min. Further optionally, the nitrogen flow rate F2 is from 95L/min to 105L/min.
By introducing nitrogen with the flow rate of 90L/min-110L/min, the lithium iron phosphate can be ensured to fully react with the reducing agent, phosphate radicals in the lithium iron phosphate are thermally decomposed into phosphorus oxide at high temperature, and lithium elements in the lithium iron phosphate generate lithium carbonate; but also can save cost and reduce energy consumption. If the nitrogen flow is less than 90L/min, the lithium iron phosphate and the reducing agent can not be fully reacted, and the recovery rate of lithium is reduced; if the nitrogen flow is more than 110L/min, the nitrogen is introduced too much, the cost is increased, and the energy consumption is increased.
Optionally, the lithium iron phosphate and the reducing agent may be placed in a tube furnace, and nitrogen gas is introduced to perform heating treatment to obtain lithium carbonate and phosphorus oxide.
And S300, mixing the lithium carbonate and the phosphorus oxide with an alkaline solution for reaction, and performing solid-liquid separation to obtain the lithium carbonate and a solution containing phosphate radicals.
In this embodiment, an alkaline solution is further provided, so that the alkaline solution and the phosphorus oxide are mixed and reacted to obtain a solution containing phosphate. Alternatively, the alkaline solution includes, but is not limited to, an alkaline solution containing ammonium ions, lithium hydroxide, and the like.
Mixing lithium carbonate, phosphorus oxide and an alkaline solution to react to generate lithium carbonate and a solution containing phosphate radical. Wherein, the phosphorus oxide is dissolved in water to generate phosphoric acid, and the phosphoric acid is mixed with the alkaline solution to react to generate a solution containing phosphate radicals. However, since lithium carbonate is hardly soluble in water, lithium carbonate is separated from a solution containing a phosphate group by means of solid-liquid separation to obtain lithium carbonate, thereby achieving separation of lithium carbonate from phosphorus impurities.
It is also understood that lithium carbonate is separated from the phosphorus impurities by leaching the lithium carbonate with the phosphorus oxide using an alkaline solution.
In summary, the method for recovering the waste lithium iron phosphate battery positive electrode material provided by the embodiment is simple, low in cost and high in operability. The alkaline solution is mixed and reacted with lithium carbonate and phosphorus oxide to remove phosphorus impurities generated in the process of recovering lithium carbonate from lithium iron phosphate, thereby improving the purity of lithium carbonate recovered from lithium iron phosphate.
Referring to fig. 2, fig. 2 is a process flow diagram included in S200 and S300 according to an embodiment of the present disclosure. In S200, the step of heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide includes:
s210, heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain the lithium carbonate, the phosphorus oxide and the iron.
The lithium iron phosphate in the present embodiment is doped with iron ions. For example, when lithium iron phosphate is derived from a positive electrode material of a waste lithium ion battery, the lithium iron phosphate material is usually doped with iron ions. Heating lithium iron phosphate and a reducing agent, and reducing iron ions in the lithium iron phosphate into iron by the reducing agent in a reducing atmosphere or a protective atmosphere in the process of reacting the lithium iron phosphate with the reducing agent; phosphate radicals in the lithium iron phosphate are thermally decomposed into phosphorus oxide at high temperature; lithium element in the lithium iron phosphate generates lithium carbonate. Since iron, phosphorus oxide, and lithium carbonate are all solids, iron, phosphorus oxide, and lithium carbonate are mixed with each other and cannot be separated at this time. In other words, lithium carbonate is doped with phosphorus impurities, as well as iron.
At S300, the step of mixing and reacting the lithium carbonate and the phosphorus oxide with an alkaline solution includes:
and S310, mixing the lithium carbonate, the phosphorus oxide and the iron with an alkaline solution, and carrying out solid-liquid separation to obtain the lithium carbonate, the iron and the solution containing the phosphate radical.
In this embodiment, an alkaline solution is further provided, so that the alkaline solution and the phosphorus oxide are mixed and reacted to obtain a solution containing phosphate. Optionally, the alkaline solution contains ammonium ions. Further optionally, the alkaline solution includes, but is not limited to, ammonia, ammonium carbonate, and the like.
Mixing iron, lithium carbonate, and phosphorus oxide with the alkaline solution and reacting to form iron, lithium carbonate, and a solution containing phosphate. Wherein, the phosphorus oxide is dissolved in water to generate phosphoric acid, and the phosphoric acid is mixed with the alkaline solution to react to generate a solution containing phosphate radicals. However, since lithium carbonate is hardly soluble in water and the alkali solution and iron do not react with each other, iron and lithium carbonate are separated from the solution containing phosphate groups by solid-liquid separation to obtain iron and lithium carbonate, thereby separating lithium carbonate from phosphorus impurities.
In one embodiment, the iron ion in the lithium iron phosphate is present in an amount of about 30% by mass of the lithium iron phosphate. However, in the present embodiment, since iron ions in lithium iron phosphate can be reduced to iron by heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere, the recovery of lithium carbonate in the subsequent step is not affected. In addition, an alkali leaching or pretreatment method can be adopted to reduce the content of iron ions in the lithium iron phosphate and further reduce the probability of interference of the iron ions on subsequent recovery of lithium carbonate.
In one embodiment, the alkaline solution satisfies at least one of the following conditions: the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is (3-4): 1; the pH value of the alkaline solution is 9-11. The solute of the alkaline solution herein refers to the amount of the chemical used to prepare the alkaline solution. In other words, the solute of the alkaline solution includes an alkaline substance, and the molar ratio of the alkaline substance to the lithium iron phosphate is (3-4): 1.
optionally, the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is (3.2-3.8): 1; further optionally, a molar ratio of a solute of the alkaline solution to the lithium iron phosphate is (3.4-3.6): 1.
the method comprises the following steps of enabling the molar ratio of a solute of an alkaline solution to lithium iron phosphate to be (3-4): 1, not only can ensure that the alkaline solution and the phosphoric acid can fully react to remove phosphorus impurities; and can reduce the material loss, practice thrift the cost. If the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is less than 3, the content of the alkaline solution is too low, the alkaline solution and the phosphoric acid cannot be ensured to be fully reacted, the probability of phosphorus impurity residue is high, and the purity of lithium carbonate is reduced; if the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is greater than 4, the content of the alkaline solution is too high, the material loss is increased, and the cost is increased.
Optionally, the pH of the alkaline solution is 9.5-10.5; further optionally, the pH of the alkaline solution is 9.8-10.2.
By limiting the pH value of the alkaline solution to 9-11, the alkaline solution and phosphoric acid can be ensured to be fully reacted to remove phosphorus impurities; but also can ensure that the alkaline solution does not react with the metal, thereby reducing the probability of introducing new impurities. If the pH value is less than 9, the alkalinity of the alkaline solution is too weak, the sufficient reaction between the alkaline solution and phosphoric acid cannot be ensured, the probability of phosphorus impurity residue is higher, and the purity of lithium carbonate is reduced; if the pH is more than 11, the alkaline solution is rendered excessively alkaline, resulting in easy reaction of the alkaline solution with the metal, thereby introducing new impurities, such as iron ions, and thus reducing the purity of lithium carbonate.
In one embodiment, when the alkaline solution contains ammonium ions, the phosphate-containing solution is an ammonium phosphate solution, and the ammonium phosphate solution is used to prepare a phosphate-containing solution, and thus the lithium iron phosphate.
The present embodiment provides an alkaline solution containing ammonium ions to obtain an ammonium phosphate solution. Alternatively, the alkaline solution containing ammonium ions includes, but is not limited to, ammonia, ammonium carbonate, and the like.
Dissolving phosphorus oxide in water to generate phosphoric acid, and mixing the phosphoric acid and an alkaline solution containing ammonium ions to react to generate an ammonium phosphate solution. The ammonium phosphate solution can be recycled. The ammonium phosphate solution is used for preparing a solution containing phosphate radicals and then is directly recycled in the new energy industry as a phosphorus source for preparing lithium iron phosphate. And the ammonium ions can be evaporated, recovered and reused after subsequent evaporation and concentration. It should be noted that the contents of the evaporation and concentration step will be described in detail later.
Wherein, the content of metal elements doped in the lithium iron phosphate is low, for example, the content of aluminum ions in the lithium iron phosphate is 1500-2000ppm; due to the fact that the content of metal elements in the lithium iron phosphate is low, the recovery method for the waste lithium iron phosphate battery positive electrode material provided by the embodiment is adopted for treatment, and the follow-up recovery of lithium carbonate cannot be influenced. In addition, an alkali leaching or pretreatment method can be adopted to reduce the content of metal elements in the lithium iron phosphate and further reduce the probability of interference of metal ions on subsequent recovery of lithium carbonate.
Optionally, the lithium iron phosphate is doped with aluminum ions. For example, when lithium iron phosphate is derived from a positive electrode material of a waste lithium ion battery, the lithium iron phosphate material is usually doped with aluminum ions.
At this time, in S100, after the step of providing lithium iron phosphate, lithium iron phosphate is subjected to alkali leaching treatment to remove aluminum ions in the lithium iron phosphate.
According to the embodiment, the aluminum ions in the lithium iron phosphate are removed by adopting an alkali leaching treatment mode, so that the probability that the aluminum ions are mixed in the lithium iron phosphate is reduced, and the probability that the aluminum ions interfere with the subsequent recovery of lithium carbonate is reduced.
Or, after the step of providing lithium iron phosphate, performing pretreatment on the lithium iron phosphate to reduce the content of aluminum ions and/or iron ions in the lithium iron phosphate at S100.
In one embodiment, during the mixing of the lithium carbonate, the phosphorus oxide, and the iron with the alkaline solution, the temperature T1 of the alkaline solution is 60 ℃ to 90 ℃ and the mixing time T1 is 0.5h to 1h.
The solubility of lithium carbonate is reduced along with the increase of the temperature, so that the mixing reaction of the alkaline solution with the temperature ranging from 60 ℃ to 90 ℃ with the iron, the lithium carbonate and the phosphorus oxide is adopted, the solubility of the lithium carbonate in the alkaline solution with the temperature ranging from 60 ℃ to 90 ℃ is reduced, the dissolution loss of the lithium carbonate is reduced, and the recovery rate of the lithium carbonate is improved. In addition, the alkaline solution with the temperature ranging from 60 ℃ to 90 ℃ is adopted to be mixed and reacted with the iron, the lithium carbonate and the phosphorus oxide, the reaction of the alkaline solution and the phosphoric acid can be accelerated along with the increase of the temperature of the alkaline solution, and the recovery efficiency of the lithium carbonate is improved.
And the short mixing time is 0.5h-1h, so that the alkaline solution and the phosphoric acid can be ensured to fully react in the time to remove phosphorus impurities, and the probability of reaction of the alkaline solution and metal caused by the overlong mixing time can be reduced.
Optionally, the temperature T1 of the alkaline solution is 65 ℃ to 85 ℃; further optionally, the temperature T1 of the basic solution is from 70 ℃ to 80 ℃.
The temperature of the alkaline solution is limited to 60-90 ℃, so that the solubility of lithium carbonate is low, and the recovery rate of lithium carbonate is improved; moreover, the reaction probability of the alkaline solution and the metal can be reduced, and the energy consumption is reduced. If the temperature is lower than 60 ℃, the solubility of the lithium carbonate is higher, the dissolution loss of the lithium carbonate is more, and the recovery rate of the lithium carbonate is reduced; if the temperature is higher than 90 ℃, the reaction probability of the alkaline solution and the metal is easily improved, new impurities are easily introduced, and the energy consumption is increased.
Optionally, the mixing time t1 of the alkaline solution is 0.6h-0.9h; further alternatively, the mixing time t1 of the alkaline solution is between 0.7h and 0.8h.
The mixing time of the alkaline solution is 0.5h-1h, so that the alkaline solution and phosphoric acid can be fully reacted to remove phosphorus impurities; and the probability of reaction of the alkaline solution and the metal caused by too long mixing time can be reduced. If the time is less than 0.5h, the reaction between the alkaline solution and the phosphoric acid is short, and the reaction cannot be fully carried out to remove phosphorus impurities; if the temperature is higher than 1h, the contact time of the alkaline solution and the metal is too long, the reaction probability of the alkaline solution and the metal is easily increased, and new impurities are easily introduced.
Referring to fig. 3, fig. 3 is a process flow chart of a method for recovering a positive electrode material of a waste lithium iron phosphate battery according to another embodiment of the present disclosure. In S310, the method includes the steps of mixing the lithium carbonate, the phosphorus oxide, and the iron with an alkaline solution, and performing solid-liquid separation to obtain the lithium carbonate, the iron, and the solution containing a phosphate group, and then:
s400, mixing and reacting the lithium carbonate, the iron and a solution containing carbonate, and carrying out solid-liquid separation to obtain the iron and a lithium bicarbonate solution.
The present embodiment also provides a carbonate-containing solution to convert lithium carbonate to lithium bicarbonate that is readily soluble in water. Alternatively, the carbonate-containing solution includes, but is not limited to, carbonic acid solution, ammonium carbonate, and the like.
Mixing iron, lithium carbonate and a solution containing carbonate to react to generate an iron and lithium bicarbonate solution. Wherein, lithium carbonate and a solution containing carbonate are mixed and reacted to produce a lithium bicarbonate solution. Lithium carbonate is poorly soluble in water, and lithium bicarbonate is readily soluble in water. Therefore, lithium carbonate is converted into lithium bicarbonate, so that preferential leaching of lithium can be achieved, and the recovery rate of lithium carbonate can be further improved. However, since iron is poorly soluble in water, and a carbonate-containing solution does not react with iron. Therefore, the iron is separated from the lithium bicarbonate solution by a solid-liquid separation mode to obtain the lithium bicarbonate solution for further purification.
Alternatively, in one embodiment, the iron, the lithium carbonate and the carbonate-containing solution are mixed, reacted and stirred so that the iron, the lithium carbonate and the carbonate-containing solution are sufficiently contacted, the reaction speed is increased, and the lithium carbonate recovery efficiency is improved.
It is also understood that the lithium bicarbonate solution is obtained by leaching iron and lithium carbonate with a solution containing carbonate.
And S500, evaporating and concentrating the lithium bicarbonate solution to obtain lithium carbonate with preset purity.
After evaporation concentration of the lithium bicarbonate solution, further purified lithium carbonate can be obtained. Compared with the lithium carbonate obtained in S300, the lithium carbonate obtained after soaking in the carbonate-containing solution and evaporating and concentrating is higher in purity. In addition, because phosphorus impurities are removed in S300, separation of iron is realized in S400, and the purity of lithium carbonate is further improved.
In one embodiment, the preset purity P of the lithium carbonate of the preset purity is 99.3% to 99.8%. Optionally, the preset purity P of the lithium carbonate with the preset purity is 99.4% -99.7%; further optionally, the preset purity of the lithium carbonate with the preset purity satisfies that P is 99.5% -99.6%.
Compared with the method for recovering lithium carbonate in the related art, in the embodiment, the phosphorus impurities are removed by using the alkaline solution, the lithium carbonate is soaked in the solution containing carbonate, and the iron and the lithium carbonate are separated, so that the high-purity lithium carbonate is recovered from the lithium iron phosphate, and the purity of the recovered lithium carbonate is 99.3% -99.8%.
Alternatively, in one embodiment, during the evaporation concentration of the lithium bicarbonate solution, the temperature T3 of the lithium bicarbonate solution is 90-100 ℃, and the time T4 of the evaporation concentration is 0.5-3 h.
Optionally, in an embodiment, the step of evaporating and concentrating the lithium bicarbonate solution to obtain lithium carbonate with a preset purity includes:
and evaporating and concentrating the lithium bicarbonate solution, and filtering, washing and drying to obtain lithium carbonate with preset purity.
The lithium bicarbonate solution is evaporated, concentrated and filtered, so that trace phosphorus, iron, phosphorus and the like can be filtered, impurities doped in the lithium carbonate can be further removed, and the purity of the lithium carbonate can be further improved. And subsequently, washing and drying the lithium carbonate by using deionized water, thereby obtaining the lithium carbonate with preset purity.
Optionally, in an embodiment, during the washing of the lithium carbonate, the lithium carbonate is washed 1 to 3 times with deionized water, and the temperature T4 of the deionized water is 80 ℃ to 100 ℃.
In an embodiment, in the process of heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide, the heating temperature T2 is 710 ℃ to 850 ℃, and the heating time T2 is 3h to 12h.
Optionally, the heating temperature T2 is 730-830 ℃; further optionally, the heating temperature T2 is 750 ℃ 800 ℃. For example, the heating temperature T2 is 720 ℃, or 740 ℃, or 760 ℃, or 780 ℃, or 820 ℃, or 840 ℃.
By limiting the temperature of the heated lithium iron phosphate and the reducing agent to 710-850 ℃, the lithium iron phosphate and the reducing agent can be ensured to fully react, lithium is converted into lithium carbide for subsequent recovery, and phosphorus is converted into phosphorus oxide for subsequent removal; but also saves materials and reduces energy consumption. If the temperature is lower than 710 ℃, iron ions in the lithium iron phosphate cannot be reduced into iron, so that the lithium carbonate is doped with the iron ions, the purity of the lithium carbonate is reduced, and the subsequent removal of phosphorus impurities is not facilitated; if the temperature is higher than 850 ℃, materials are easily wasted, and energy consumption is increased. For example, when the reducing agent is carbon powder, lithium iron phosphate and the carbon powder are put in nitrogen to be combusted, and if the temperature is lower than 710 ℃, carbon monoxide is generated from the carbon powder, and the carbon powder cannot be sufficiently converted into carbon dioxide, so that phosphorus cannot be sufficiently converted into phosphorus oxide. If the temperature is higher than 850 ℃, materials are easily wasted, and energy consumption is increased.
Optionally, in an embodiment, during the temperature raising process, the temperature is raised from the normal temperature to 710 ℃ to 850 ℃ at the speed of 1 ℃/min to 10 ℃/min and is kept for 3 to 12 hours, and then the lithium carbonate and the phosphorus oxide are naturally cooled to the normal temperature. This embodiment is through slowly rising temperature, the process of slow cooling, ensures that lithium iron phosphate and reductant fully react, but also can not cause too big temperature variation for heating device, like the tube furnace, has reduced the probability of damaging the heating device.
Optionally, the heating time t2 is 4h-11h; further optionally, the heating time t2 is 5h to 10h.
By limiting the heating time for heating the lithium iron phosphate and the reducing agent to 3-12h, the lithium iron phosphate can be ensured to fully react with the reducing agent, lithium is converted into lithium carbide for subsequent recovery, and phosphorus is converted into phosphorus oxide for subsequent removal; but also saves materials and reduces energy consumption. If the heating time is less than 3h, the lithium iron phosphate and the reducing agent cannot fully react, so that phosphorus is doped in lithium carbonate, the purity of the lithium carbonate is reduced, and the subsequent removal of phosphorus impurities is not facilitated; if the heating time is longer than 12 hours, the material is easily wasted, and the energy consumption is increased.
In one embodiment, when the reducing agent contains carbon, heating the lithium iron phosphate and the reducing agent containing carbon in the reducing atmosphere or the protective atmosphere also produces carbon dioxide, which is used to prepare the carbonate-containing solution.
The reducing agent provided in the present embodiment contains carbon element so that the heating process generates both lithium carbonate and phosphorus oxide and carbon dioxide. The reducing agent containing carbon element includes but is not limited to carbon powder, carbon monoxide, etc.
During the reaction of the lithium iron phosphate with the reducing agent containing the carbon element, the reducing agent containing the carbon element produces carbon dioxide, which can be used to prepare the solution containing carbonate for the subsequent mixed reaction of the iron, and the lithium carbonate with the solution containing carbonate in S400. Therefore, the embodiment not only reduces the exhaust emission and thus the environmental pollution, but also realizes the recycling of resources by recycling the carbon dioxide exhaust.
Referring to fig. 4, fig. 4 is a process flow chart included in S310 according to an embodiment of the present disclosure. Wherein after the mixing and reacting the lithium carbonate and the iron with the carbonate-containing solution at S310, the method comprises:
s311, introducing carbon dioxide into the solution containing carbonate, wherein the flow rate F1 of the carbon dioxide is 5L/min-60L/min.
When a carbonate-containing solution prepared from carbon dioxide obtained by heating lithium iron phosphate and a reducing agent containing carbon element in S200 is mixed with iron and lithium carbonate, carbon dioxide is introduced to ensure that sufficient carbonate in the carbonate-containing solution reacts with lithium carbonate to generate lithium bicarbonate.
Optionally, the flow rate of carbon dioxide F1 is 10L/min-50L/min; further optionally, the carbon dioxide flow rate F1 is from 20L/min to 40L/min.
By limiting the flow rate of the carbon dioxide to 5L/min-60L/min, sufficient carbonate in the solution containing the carbonate can be ensured to react with lithium carbonate to generate lithium bicarbonate; but also saves materials and reduces energy consumption. If the flow rate is less than 5L/min, the carbonate in the solution containing carbonate is less, so that the solution containing carbonate cannot fully react with lithium carbonate, and the leaching of lithium is not facilitated; if the flow rate is more than 60L/min, the material is easily wasted and the energy consumption is increased.
Alternatively, in one embodiment, during the mixing reaction of the iron, and the lithium carbonate and the carbonate-containing solution, the concentration c2 of the carbonate-containing solution is 0.4mol/L-1mol/L, and the mixing time t3 is 0.5h-3h.
Optionally, the concentration c2 of the carbonate-containing solution is 0.5mol/L to 0.9mol/L; further optionally, the concentration c2 of the carbonate-containing solution is in the range of 0.6mol/L to 0.7mol/L.
By limiting the concentration of the solution containing carbonate to 0.4mol/L-1mol/L, not only can enough carbonate in the solution containing carbonate be ensured to react with lithium carbonate to generate lithium bicarbonate; but also saves materials and reduces energy consumption. If the concentration of the carbonate-containing solution is less than 0.4mol/L, the carbonate in the carbonate-containing solution is less, the carbonate-containing solution cannot sufficiently react with lithium carbonate, and the lithium leaching is not facilitated; if the concentration of the carbonate-containing solution is more than 1mol/L, materials are easily wasted and energy consumption is increased.
Optionally, the mixing time t3 is 1h to 2.5h; further alternatively, the mixing time t3 is from 1.5h to 2h.
By limiting the mixing time to 0.5h-3h, not only can the solution containing carbonate be ensured to fully react with lithium carbonate to generate lithium bicarbonate; but also improves the recovery efficiency and reduces the energy consumption. If the mixing time is less than 0.5h, the reaction time is short, so that the solution containing carbonate cannot fully react with lithium carbonate, and lithium leaching is not facilitated; if the mixing time is more than 3 hours, the recovery efficiency tends to be lowered and the energy consumption also tends to be increased.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the progress of the method for recovering the cathode material of the waste lithium iron phosphate battery obvious, the above technical solution is illustrated by a plurality of examples.
Example 1:
step 1: collecting waste lithium iron phosphate materials, crushing the waste lithium iron phosphate materials by using a mechanical crusher, adding carbon powder, and uniformly stirring, wherein the mass of the carbon powder is 5% of that of the lithium iron phosphate.
Step 2: placing the waste lithium iron phosphate and carbon powder treated in the step 1 into a tubular furnace, heating to 710 ℃ from normal temperature at the speed of 1-10 ℃/min under the environment of nitrogen flow rate of 90L/min, and keeping the temperature for 12h; then naturally cooling to normal temperature, and recovering carbon dioxide into deionized water to prepare carbonated water.
And step 3: and (3) filtering and washing the waste lithium iron phosphate reduction products (iron, lithium carbonate and phosphorus pentoxide) obtained in the step (2) for 1h by using an ammonia-alkali solution, wherein the temperature of the ammonia-alkali solution is 90 ℃, and the molar ratio of the solute of the ammonia-alkali solution to the lithium iron phosphate is 3.
And 4, step 4: and (3) leaching the filter washing slag (iron and lithium carbonate) in the step (3) by using the carbonic water prepared in the step (2) for 3 hours under stirring, introducing carbon dioxide at the speed of 5L/min, and filtering to obtain a slag containing Fe and Al and a solution containing lithium bicarbonate.
And 5: and (5) evaporating and concentrating the lithium bicarbonate solution obtained in the step (4) at 90 ℃ for 3 hours, filtering, washing filter residues with deionized water at 80 ℃ for 1-3 times, and drying to obtain the lithium carbonate with the purity of 99.3%.
Example 2:
step 1: collecting waste lithium iron phosphate materials, crushing the waste lithium iron phosphate materials by using a mechanical crusher, adding carbon powder, and uniformly stirring, wherein the mass of the carbon powder is 10% of that of the lithium iron phosphate.
Step 2: placing the waste lithium iron phosphate and carbon powder treated in the step 1 into a tubular furnace, heating to 850 ℃ from normal temperature at the speed of 1-10 ℃/min under the environment of 110L/min of nitrogen flow, and preserving heat for 3h; then naturally cooling to normal temperature, and recovering carbon dioxide to deionized water to prepare carbonated water.
And 3, step 3: and (3) filtering and washing the waste lithium iron phosphate reduction product (iron, lithium carbonate and phosphorus pentoxide) obtained in the step (2) for 0.5h by using an ammonia-alkali solution, wherein the temperature of the ammonia-alkali solution is 60 ℃, and the molar ratio of the solute of the ammonia-alkali solution to the lithium iron phosphate is 4.
And 4, step 4: and (3) stirring and leaching the filter washing slag (iron and lithium carbonate) obtained in the step (3) for 0.5h by using the carbonated water prepared in the step (2), introducing carbon dioxide at the rate of 60L/min, and filtering to obtain a slag containing Fe and Al and a lithium bicarbonate-containing solution.
And 5: and (5) evaporating and concentrating the lithium bicarbonate solution obtained in the step (4) at 100 ℃ for 0.5h, filtering, washing filter residues with deionized water at 100 ℃ for 1-3 times, and drying to obtain the lithium carbonate with the purity of 99.8%.
Example 3:
step 1: collecting waste lithium iron phosphate materials, crushing the waste lithium iron phosphate materials by using a mechanical crusher, adding carbon powder, and uniformly stirring, wherein the mass of the carbon powder is 8% of that of the lithium iron phosphate.
Step 2: placing the waste lithium iron phosphate and carbon powder treated in the step 1 into a tubular furnace, heating to 550 ℃ from normal temperature at the speed of 1-10 ℃/min under the environment of 100L/min of nitrogen flow, and preserving heat for 8 hours; then naturally cooling to normal temperature, and recovering carbon dioxide into deionized water to prepare carbonated water.
And step 3: and (3) filtering and washing the waste lithium iron phosphate reduction product (iron, lithium carbonate and phosphorus pentoxide) obtained in the step (2) for 0.7h by using an ammonia-alkali solution, wherein the temperature of the ammonia-alkali solution is 75 ℃, and the molar ratio of the solute of the ammonia-alkali solution to the lithium iron phosphate is 3.5.
And 4, step 4: and (3) leaching the filter washing slag (iron and lithium carbonate) in the step (3) by using the carbonic water prepared in the step (2) for 1.5 hours under stirring, introducing carbon dioxide at the speed of 30L/min, and filtering to obtain a slag recovery containing Fe and Al and a lithium bicarbonate-containing solution.
And 5: and (4) evaporating and concentrating the lithium bicarbonate solution obtained in the step (4) at 95 ℃ for 1.5h, filtering, washing filter residues with deionized water at 90 ℃ for 1-3 times, and drying to obtain the lithium carbonate with the purity of 99.6%.
As can be seen from the foregoing examples 1 to 3, the preparation methods of examples 1 to 3 provided in the present application can effectively remove phosphorus impurities, so that the prepared lithium carbonate has high purity.
The foregoing detailed description has provided for the embodiments of the present application, and the principles and embodiments of the present application have been presented herein for purposes of illustration and description only and to facilitate understanding of the methods and their core concepts; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. A method for recovering a positive electrode material of a waste lithium iron phosphate battery is characterized by comprising the following steps:
providing lithium iron phosphate and a reducing agent;
heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide;
and mixing the lithium carbonate and the phosphorus oxide with an alkaline solution for reaction, and carrying out solid-liquid separation to obtain the lithium carbonate and a solution containing phosphate radicals.
2. The method for recovering the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the step of heating the lithium iron phosphate and the reducing agent in a reducing atmosphere or a protective atmosphere to obtain lithium carbonate and phosphorus oxide comprises the following steps:
heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain the lithium carbonate, the phosphorus oxide and the iron;
the step of mixing and reacting the lithium carbonate and the phosphorus oxide with an alkaline solution comprises the following steps:
and mixing the lithium carbonate, the phosphorus oxide and the iron with an alkaline solution, and carrying out solid-liquid separation to obtain the lithium carbonate, the iron and the solution containing phosphate radicals.
3. The method for recycling the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 2, wherein the alkaline solution satisfies at least one of the following conditions:
the molar ratio of the solute of the alkaline solution to the lithium iron phosphate is (3-4): 1;
the pH value of the alkaline solution is 9-11.
4. The method for recycling the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 2, wherein when the alkaline solution contains ammonium ions, the solution containing phosphate is an ammonium phosphate solution, and the ammonium phosphate solution is used for preparing a solution containing phosphate, so as to prepare the lithium iron phosphate.
5. The method for recycling the positive electrode material of the waste lithium iron phosphate batteries according to claim 2, wherein in the process of mixing the lithium carbonate, the phosphorus oxide and the iron with the alkaline solution, the temperature T1 of the alkaline solution is 60-90 ℃, and the mixing time T1 is 0.5-1 h.
6. The method for recovering the positive electrode material of the waste lithium iron phosphate batteries according to claim 2, wherein the method comprises, after the steps of mixing the lithium carbonate, the phosphorus oxide, and the iron with an alkaline solution, and performing solid-liquid separation to obtain the lithium carbonate, the iron, and the solution containing phosphate groups, the steps of:
mixing and reacting the lithium carbonate, the iron and a solution containing carbonate, and performing solid-liquid separation to obtain the iron and a lithium bicarbonate solution;
and evaporating and concentrating the lithium bicarbonate solution to obtain lithium carbonate with preset purity.
7. The method for recycling the positive electrode material of the waste lithium iron phosphate batteries according to claim 6, wherein the preset purity P of the lithium carbonate is 99.3% -99.8%.
8. The method for recycling the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein in the process of heating the lithium iron phosphate and the reducing agent in the reducing atmosphere or the protective atmosphere to obtain the lithium carbonate and the phosphorus oxide, the heating temperature T2 is 710 ℃ to 850 ℃, and the heating time T2 is 3h to 12h.
9. The method for recycling the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 6, wherein when the reducing agent contains carbon, the lithium iron phosphate and the reducing agent containing carbon are heated in the reducing atmosphere or the protective atmosphere to obtain carbon dioxide, and the carbon dioxide is used for preparing the solution containing carbonate.
10. The method for recycling the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 9, wherein after the mixing reaction of the lithium carbonate and the iron with the solution containing carbonate, the method comprises the following steps:
and introducing carbon dioxide into the carbonate-containing solution, wherein the flow rate F1 of the carbon dioxide is 5L/min-60L/min.
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