CN116723999A - A kind of repair and regeneration method of lithium iron phosphate - Google Patents
A kind of repair and regeneration method of lithium iron phosphate Download PDFInfo
- Publication number
- CN116723999A CN116723999A CN202380008814.7A CN202380008814A CN116723999A CN 116723999 A CN116723999 A CN 116723999A CN 202380008814 A CN202380008814 A CN 202380008814A CN 116723999 A CN116723999 A CN 116723999A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- repair
- regeneration method
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a repairing and regenerating method of lithium iron phosphate, and belongs to the technical field of lithium ion batteries. Crushing, soaking, screening, ball milling and sorting lithium iron phosphate waste pole pieces to obtain lithium iron phosphate waste pole pieces, roasting the lithium iron phosphate waste pole pieces at the temperature of 750-900 ℃ in a carbon dioxide atmosphere, uniformly stirring the obtained roasting product and water, introducing carbon dioxide, and carrying out spray granulation on a mixture obtained by reaction to obtain a lithium iron phosphate precursor; and finally calcining the obtained lithium iron phosphate precursor to obtain regenerated lithium iron phosphate. According to the method for repairing and regenerating the lithium iron phosphate, a carbon source, a phosphorus source and a lithium source do not need to be added, the carbon content in the prepared regenerated lithium iron phosphate is less than 0.15%, the Al content is less than 0.015%, and the charging and discharging capacity is high.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a repairing and regenerating method of lithium iron phosphate.
Background
With the increasing global energy shortage and environmental disruption, reducing resource consumption and protecting the environment is becoming a widespread consensus. The lithium ion battery is widely applied to electric automobiles and various electronic equipment due to the advantages of high energy density, high voltage, good cycle performance, low self-discharge, environmental protection and the like, and a good side is found for people to jump out of the energy shortage dilemma. The lithium iron phosphate battery has the advantages of low cost, safety, good thermal stability, high cycle performance and the like, and has a large market share in lithium batteries. The service cycle of the lithium iron phosphate battery is 5-7 years, a large number of lithium iron phosphate batteries are retired at present and are continuously increased in the future, so that waste LiFePO is recovered 4 The research work on batteries is urgent.
LiFePO 4 The positive electrode material accounts for about 40% of the cost of the battery, and the high-valued recovery of the positive electrode material has higher economic value. To date, for waste LiFePO 4 The recovery and disposal mode of the anode material mainly comprises repair regeneration and hydrometallurgy; in the prior art, oxygen or air is used for carrying out high-temperature sintering separation treatment on the positive plate, the content of Al, F and other impurities in the separated lithium iron phosphate waste electrode powder is high, the residual quantity of metal simple substances is large, and LiFePO is prepared 4 The lithium source, the iron source and the phosphorus source are required to be supplemented in the precursor sintering process, meanwhile, fluoride generated by pyrolysis of the binder can react with aluminum or lithium iron phosphate, and generated lithium fluoride and aluminum fluoride enter the positive electrode material, so that the stability of the regenerated product is restricted.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a method for repairing and regenerating lithium iron phosphate.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows: the method for repairing and regenerating the lithium iron phosphate comprises the following steps:
s1: ball milling and sorting are carried out on the lithium iron phosphate waste pole piece to obtain lithium iron phosphate waste pole powder;
s2: roasting the lithium iron phosphate waste electrode powder obtained in the step S1 at 750-900 ℃ in a carbon dioxide atmosphere, uniformly stirring the obtained roasting product and water, introducing carbon dioxide, and performing spray granulation on a mixture obtained by reaction to obtain a lithium iron phosphate precursor;
s3: and (3) adding the lithium iron phosphate precursor obtained in the step (S2) into an atmosphere furnace, and calcining at 550-750 ℃ under the protection of inert gas to obtain regenerated lithium iron phosphate.
In the repairing and regenerating method of the application, CO is used for 2 As a reaction atmosphere, PVDF is cracked into carbon at high temperature, and conductive carbon black is changed into CO, achieving the purpose of F removal and carbon removal. Crushing the lithium iron phosphate waste sheet, soaking the crushed lithium iron phosphate waste sheet in hot water, separating aluminum slag from battery black powder in the waste sheet by soaking, and sieving the waste sheet by using a water sieve, wherein the oversize product is the aluminum slag, and the undersize product is a mixture of the battery black powder and the aluminum slag; the obtained undersize is ball-milled and then separated, so that part of Al in the lithium iron phosphate waste electrode powder can be separated; roasting can convert Al in the lithium iron phosphate waste electrode powder into aluminum oxide; after the roasting product and water are evenly stirred, carbonic acid generated by introducing carbon dioxide can further remove Al in the roasting product, and the specific reaction has the chemical formula of H 2 O+CO 2 →H 2 CO 3 ，3H 2 CO 3 +2Al→Al 2 (CO 3 ) 3 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the The above steps act together to reduce Al impurity in regenerated lithium iron phosphate to the maximum extent, and metal impurities brought in other alkali lye aluminum removing methods are not introduced, so that the safety of the battery is ensured. In addition, willAfter the roasting product is uniformly mixed with water, introducing carbon dioxide for reaction, so that the roasting product is weakly dissolved, aluminum is removed by filtration, and the consumption of residual carbon, the in-situ wrapping of Al and the sphericizing regeneration of lithium iron phosphate can be realized by combining a spray drying mode; the regenerated lithium iron phosphate can be obtained directly through calcination without adding a lithium source, an iron source and a phosphorus source.
The roasting temperature is one of key factors influencing the removing effect of Al, carbon, F and other impurities in the lithium iron phosphate waste electrode powder, if the roasting temperature is too low, the Al, carbon, F and other impurities in the lithium iron phosphate waste electrode powder cannot be completely converted into other removable substances, such as Al cannot be completely converted into alumina, and carbon cannot be completely converted into CO; if the firing temperature is too high, decomposition of lithium iron phosphate may occur.
The lithium iron phosphate waste pole piece comprises a scrapped positive pole piece in the manufacturing process of the lithium iron phosphate positive pole piece, a positive pole piece decomposed from a battery scrapped without electrolyte injection in the battery manufacturing process, and a lithium iron phosphate positive pole piece disassembled from various scrapped batteries.
As a further improvement of the application, in the step S2, the temperature rising rate of the roasting temperature is 2-5 ℃/min.
The temperature rising rate of the roasting temperature is too fast, so that the service life of the atmosphere furnace is easy to damage, and the experimental efficiency is influenced by the too slow temperature rising rate of the roasting temperature, and the temperature rising rate in the range can effectively improve the removal effect of impurities such as Al, carbon, F and the like in the lithium iron phosphate waste electrode powder through optimization.
As a further improvement of the application, in the step S2, the roasting time is 2-4h. In the above-mentioned roasting time range, the decomposition effect of lithium iron phosphate waste electrode powder is better.
As a further improvement of the present application, in the step S2, the preparation method of the mixture is as follows: stirring the roasting product and water uniformly, heating to 40-80 ℃, then introducing carbon dioxide, and stirring for 30-60min at the rotating speed of 200-300rpm to obtain the catalyst.
As a further improvement of the application, in the step S2, the flow rate of the carbon dioxide is 1-100L/min.
The flow rate of the carbon dioxide is 1-100L/min, so that the carbon dioxide can better react with Al in the roasting product to remove the Al in the roasting product.
As a further improvement of the present application, in step S2, the conditions of spray granulation include: the spraying is carried out under the inert protective gas, the spraying temperature is 170-190 ℃, the feeding speed is 300-650mL/h, the air inlet pressure is 0.1-0.5MPa, the outlet temperature is 120-150 ℃, and the inert protective gas is one of nitrogen, argon and helium.
According to the application, parameters such as spray temperature, feed rate, air inlet pressure and the like in spray granulation are controlled within the preferable ranges, the prepared lithium iron phosphate precursor has a better spherical structure, and the residual Al in the roasted lithium iron phosphate product can be wrapped in situ, so that the influence of Al impurities on the stability and electrical performance of the product is avoided, the content of Al in regenerated lithium iron phosphate is reduced, and the electrical performance and stability of the battery are further improved.
As a further improvement of the application, in the step S2, the tail gas obtained by the reaction is treated with HCl-CuCl 2 And (5) absorbing the saturated solution.
As a further improvement of the application, the step S1 is preceded by the steps of crushing, soaking and screening the lithium iron phosphate waste sheet;
as a further improvement of the application, the specific steps of crushing, soaking and screening the lithium iron phosphate waste sheet are as follows: cutting the lithium iron phosphate waste pole piece into pieces with the size of (1-2 cmx1-2 cm) by scissors; soaking the obtained pieces in hot water at 50-80deg.C for 5-60min, and sieving with 2-15 mesh sieve.
As a further improvement of the present application, in the step S1, the ball milling parameters are as follows: the ball-to-material ratio is 5-20:1, the ball milling rotating speed is 100-400rpm, and the ball milling time is 5-60min.
As a further improvement of the present application, in the step S1, the sorting is air flow sorting, and parameters of the air flow sorting are as follows: the feeding speed is 3-5kg/min, the pulsation frequency is 30-50Hz, and the air flow speed is 10-12cm/s.
According to the application, the lithium iron phosphate waste pole piece is further polished and crushed in a ball milling mode, the battery black powder and the aluminum slag can be effectively separated by optimizing and controlling the ball milling parameters, and the impurity Al content in the lithium iron phosphate waste pole piece is further reduced by the air flow sorting parameters.
As a further improvement of the application, in the step S3, the calcination time is 2-8h.
As a further improvement of the present application, in the step S3, the lithium iron phosphate precursor is further subjected to pre-sintering at 400-500 ℃ for 1-4 hours.
By utilizing a method of combining presintering and calcining, the bonding, densification, tissue structure change and rearrangement among lithium iron phosphate precursors can be realized in different temperature ranges, but no tissue dissolution exists, no new composition or new phase appears, and the obtained regenerated lithium iron phosphate can be used as a new lithium iron phosphate battery anode material.
As a further improvement of the present application, in the step S4, the pre-sintering and the calcination are performed under the protection of an inert gas, wherein the inert gas is one of nitrogen, argon and helium.
In a second aspect, the application provides lithium iron phosphate, which is prepared by the repair and regeneration method of lithium iron phosphate.
In a third aspect, the application also provides an application of the lithium iron phosphate prepared by the method for repairing and regenerating the lithium iron phosphate in preparing batteries.
Compared with the prior art, the application has the beneficial effects that:
(1) In the repairing and regenerating method of the application, CO is used for 2 As a reaction atmosphere, PVDF is cracked into carbon at high temperature, and conductive carbon black is changed into CO, so that the purposes of F removal and carbon removal are realized; the carbon content in the regenerated lithium iron phosphate is less than 0.15%.
(2) The application adopts the steps of crushing, soaking, screening, ball milling, sorting and CO 2 The method of high temperature roasting, al removal by carbonic acid and the like are combined together, so that the content of impurity Al in the regenerated lithium iron phosphate can be effectively reducedThe content is less than 0.015 percent.
(3) According to the application, after the roasting product is weakly dissolved, spray drying granulation is carried out, so that the consumption of residual carbon, in-situ wrapping of Al and sphericizing regeneration of lithium iron phosphate can be realized; the regenerated lithium iron phosphate can be obtained directly through calcination without adding a lithium source, an iron source and a phosphorus source, and the obtained regenerated lithium iron phosphate can be used as a novel lithium iron phosphate battery anode material.
Drawings
FIG. 1 is a process flow diagram of a method for repairing and regenerating lithium iron phosphate according to the present application.
Detailed Description
The present application will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present application, and the object of the present application is to be understood in detail, not to limit the present application. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present application. The experimental reagents and instruments involved in the practice of the present application are common reagents and instruments unless otherwise specified.
Example 1
The embodiment provides a repair and regeneration method of lithium iron phosphate, which comprises the following steps:
(1) Cutting the lithium iron phosphate waste pole piece into pieces with the size of 2cmx2cm by scissors; soaking the obtained fragments in hot water at 50deg.C for 5min, sieving with 2 mesh sieve, wherein the over-sieve material is aluminum slag, and the under-sieve material is mixture of black powder of battery and aluminum slag;
(2) Drying the undersize obtained in the step (1), loading the undersize into a ball milling tank, adding zirconium balls into the ball milling tank, wherein the ball-to-material ratio is 5:1, and then placing the ball milling tank on a planetary ball mill to perform ball milling for 60min at a rotating speed of 400 rpm; placing the obtained ball-milling product in a pulsating gas flow separator, setting the feeding speed of the gas flow separator to be 3kg/min, the pulsating frequency to be 30Hz and the gas flow speed to be 10cm/s, and separating part of Al in the ball-milling product to obtain lithium iron phosphate waste electrode powder;
(3) The phosphoric acid obtained in the step (2) is reacted withFilling the iron-lithium waste electrode powder into a crucible, then placing the crucible into a tube furnace and introducing CO 2 Heating to 750deg.C at a heating rate of 5deg.C/min after 60min, roasting for 240min to remove carbon impurities in the pole piece powder, and converting Al into Al 2 O 3 Removing the tail gas by HCl-CuCl 2 Absorbing the saturated solution to obtain a roasting product;
(4) Placing the roasting product obtained in the step (3) and water into a beaker, heating to 50 ℃, then introducing carbon dioxide with the flow rate of 100L/min, reacting for 60min at the stirring rotation speed of 200r/min, and filtering to remove Al to obtain a mixture;
(5) And (3) carrying out spray granulation on the mixture obtained in the step (4) to obtain a lithium iron phosphate precursor, wherein the parameters of spray granulation are as follows: the spraying temperature is 170 ℃, the feeding speed is 400mL/h, the air inlet pressure is 0.2MPa, the outlet temperature is 130 ℃, and the gas is nitrogen;
(6) And (3) filling the lithium iron phosphate precursor obtained in the step (5) into a crucible, placing the crucible into a tube furnace, passing helium gas, heating to 400 ℃ at a heating rate of 5 ℃/min after 60min, presintering for 180min, and heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining for 300min to obtain the regenerated lithium iron phosphate.
Example 2
The embodiment provides a repair and regeneration method of lithium iron phosphate, which comprises the following steps:
(1) Cutting the lithium iron phosphate waste pole piece into pieces with the size of 2cmx2cm by scissors; soaking the obtained fragments in hot water at 65deg.C for 30min, sieving with 10 mesh sieve, wherein the oversize product is aluminum residue, and the undersize product is mixture of black powder of battery and aluminum residue;
(2) Drying the undersize obtained in the step (1), loading the undersize into a ball milling tank, adding zirconium balls into the ball milling tank, wherein the ball-to-material ratio is 10:1, and then placing the ball milling tank on a planetary ball mill to perform ball milling for 180min at a rotating speed of 400 rpm; placing the obtained ball-milling product in a pulsating gas flow separator, setting the feeding speed of the gas flow separator to be 4kg/min, the pulsating frequency to be 40Hz and the gas flow speed to be 11cm/s, and separating part of Al in the ball-milling product to obtain lithium iron phosphate waste electrode powder;
(3) Filling the lithium iron phosphate waste electrode powder obtained in the step (2) into a crucibleIn a crucible, then put into a tube furnace and introduced with CO 2 Heating to 800 ℃ at a heating rate of 5 ℃/min after 30min, roasting for 180min to remove carbon impurities in the pole piece powder, and simultaneously converting Al into Al 2 O 3 Removing the tail gas by HCl-CuCl 2 Absorbing the saturated solution to obtain a roasting product;
(4) Placing the roasting product obtained in the step (3) and water into a beaker, heating to 60 ℃, then introducing carbon dioxide with the flow of 50L/min, and reacting for 50min at the stirring rotation speed of 200r/min to remove Al, so as to obtain a mixture;
(5) And (3) carrying out spray granulation on the mixture obtained in the step (4) to obtain a lithium iron phosphate precursor, wherein the parameters of spray granulation are as follows: the spraying temperature is 180 ℃, the feeding speed is 500mL/h, the air inlet pressure is 0.3MPa, the outlet temperature is 140 ℃, and the gas is nitrogen;
(6) And (3) filling the lithium iron phosphate precursor obtained in the step (5) into a crucible, placing the crucible into a tube furnace, passing helium gas, heating to 450 ℃ at a heating rate of 5 ℃/min after 90min, presintering for 120min, and heating to 600 ℃ at a heating rate of 5 ℃/min, and calcining for 240min to obtain the regenerated lithium iron phosphate.
Example 3
The embodiment provides a repair and regeneration method of lithium iron phosphate, which comprises the following steps:
(1) Cutting the lithium iron phosphate waste pole piece into pieces with the size of 2cmx2cm by scissors; soaking the obtained fragments in hot water at 80deg.C for 60min, sieving with 15 mesh sieve, wherein the over-sieve material is aluminum residue, and the under-sieve material is mixture of black powder of battery and aluminum residue;
(2) Drying the undersize obtained in the step (1), loading the undersize into a ball milling tank, adding zirconium balls into the ball milling tank, wherein the ball-to-material ratio is 15:1, and then placing the ball milling tank on a planetary ball mill to perform ball milling for 240min at a rotating speed of 400 rpm; placing the obtained ball-milling product in a pulsating gas flow separator, setting the feeding speed of the gas flow separator to be 5kg/min, the pulsating frequency to be 50Hz and the gas flow speed to be 12cm/s, and separating part of Al in the ball-milling product to obtain lithium iron phosphate waste electrode powder;
(3) Filling the lithium iron phosphate waste electrode powder obtained in the step (2) into a crucible, and then placing the crucible into a tube furnaceCO is introduced into 2 Heating to 900 ℃ at a heating rate of 5 ℃/min after 90min, roasting for 120min to remove carbon impurities in the pole piece powder, and simultaneously converting Al into Al 2 O 3 Removing the tail gas by HCl-CuCl 2 Absorbing the saturated solution to obtain a roasting product;
(4) Filling the roasting product obtained in the step (3) and water into a beaker, heating to 70 ℃, then introducing carbon dioxide with the flow of 1L/min, and reacting for 30min at the stirring rotation speed of 200r/min to remove Al, so as to obtain a mixture;
(5) And (3) carrying out spray granulation on the mixture obtained in the step (4) to obtain a lithium iron phosphate precursor, wherein the parameters of spray granulation are as follows: the spraying temperature is 190 ℃, the feeding speed is 600mL/h, the air inlet pressure is 0.4MPa, the outlet temperature is 150 ℃, and the gas is nitrogen;
(6) And (3) filling the lithium iron phosphate precursor obtained in the step (5) into a crucible, placing the crucible into a tube furnace, passing helium gas, heating to 500 ℃ at a heating rate of 5 ℃/min after 120min, presintering for 90min, and heating to 650 ℃ at a heating rate of 5 ℃/min, and calcining for 180min to obtain the regenerated lithium iron phosphate.
Comparative example 1
The comparative example provides a repair and regeneration method of lithium iron phosphate, which comprises the following steps:
(1) Cutting the lithium iron phosphate waste pole piece into pieces with the size of 2cmx2cm by scissors; soaking the obtained fragments in hot water at 80deg.C for 60min, sieving with 15 mesh sieve, wherein the over-sieve material is aluminum residue, and the under-sieve material is mixture of black powder of battery and aluminum residue;
(2) Drying the undersize obtained in the step (1), loading the undersize into a ball milling tank, adding zirconium balls into the ball milling tank, wherein the ball-to-material ratio is 15:1, and then placing the ball milling tank on a planetary ball mill to perform ball milling for 240min at a rotating speed of 400 rpm; placing the obtained ball-milling product in a pulsating gas flow separator, setting the feeding speed of the gas flow separator to be 5kg/min, the pulsating frequency to be 50Hz and the gas flow speed to be 12cm/s, and separating part of Al in the ball-milling product to obtain lithium iron phosphate waste electrode powder;
(3) And (3) filling the lithium iron phosphate waste electrode powder obtained in the step (2) into a crucible, then placing the crucible into a tube furnace, introducing air, heating to 600 ℃ at a heating rate of 5 ℃/min after 90min, roasting for 120min, wherein after roasting, the structure of the lithium iron phosphate is destroyed, ferrous iron is oxidized into ferric iron, the lithium iron phosphate waste electrode powder is changed from black into red, and if a carbon source, a phosphorus source and a lithium source are not supplemented, the lithium iron phosphate waste electrode powder is directly calcined under the protection of inert gas, so that the regenerated lithium iron phosphate cannot be obtained.
Comparative example 2
The present comparative example provides a repair regeneration method of lithium iron phosphate, which differs from example 1 only in that: the roasting temperature in the step (3) is 700 ℃, and carbon and Al in the lithium iron phosphate waste electrode powder cannot be completely removed due to the fact that the roasting temperature is too low, so that the carbon content and the Al content in the regenerated lithium iron phosphate are high.
Comparative example 3
The present comparative example provides a repair regeneration method of lithium iron phosphate, which differs from example 1 only in that: the firing temperature in step (3) was 950 ℃.
Comparative example 4
The present comparative example provides a repair regeneration method of lithium iron phosphate, which differs from example 1 only in that: in the step (4), CO is not introduced 2 。
Example 4
The content of part of elements of the regenerated lithium iron phosphate obtained in each example and comparative example is tested, wherein the content of Li, fe and Al elements is tested according to a chemical analysis method of lithium iron phosphate with the standard YS/T1028.5-2015; the content of the P element is tested according to a chemical analysis method of lithium iron phosphate with the standard YS/T1028.3-2015; the content of the C element is obtained according to a chemical analysis method of lithium iron phosphate with the test standard YS/T1028.4-2015; the test results are shown in Table 1.
TABLE 1
| Element content (%) | Li | P | Fe | Al | C |
| Example 1 | 4.44 | 19.83 | 35.84 | 0.01 | 1.50 |
| Example 2 | 4.36 | 19.61 | 35.68 | 0.01 | 1.41 |
| Example 3 | 4.52 | 20.01 | 36.23 | 0.01 | 1.20 |
| Comparative example 2 | 4.39 | 19.78 | 36.12 | 0.04 | 3.00 |
| Comparative example 3 | 4.48 | 19.89 | 36.10 | <0.01 | 0.81 |
| Comparative example 4 | 4.47 | 19.90 | 35.94 | 0.04 | 2.94 |
As can be seen from Table 1, the main elements, al and C contents in the regenerated lithium iron phosphate prepared in the examples are normal, and the regenerated lithium iron phosphate meets the industrial production standards of lithium iron phosphate batteries.
Example 5
The regenerated lithium iron phosphate obtained in each of the examples and comparative examples was made into button cells for electrochemical performance comparison study. The button cell is prepared by mixing lithium iron phosphate active substance, conductive carbon black and PCDF according to the mass ratio of 8:1:1, the materials are mixed according to the proportion to prepare slurry, the slurry is coated on aluminum foil, and the aluminum foil is baked for 8 hours at 120 ℃, and then the aluminum foil is rolled and cut to prepare small round pole pieces for manufacturing button cells. The button cell is assembled in a glove box under the conditions that the water and oxygen content is less than or equal to 0.01ppm and the electrolyte is 1.0M LiPF 6 in EC, DMC, dec=1:1:1 vol%. Test conditions for battery performance: the charge-discharge voltage is in the range of 2.5-4.2V (relative to Li + Li) at 25 ℃, and charge and discharge at 0.1C current density (1c=150 mA/g), the battery performance was obtained as shown in table 2.
TABLE 2
| Electrochemical Properties | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | First charge and discharge efficiency (%) |
| Example 1 | 158.6 | 149.9 | 94.5 |
| Example 2 | 154.9 | 145.6 | 94.0 |
| Example 3 | 156.7 | 147.5 | 94.1 |
| Comparative example 2 | 148.6 | 135.7 | 91.3 |
| Comparative example 3 | 89.6 | 68.4 | 76.3 |
| Comparative example 4 | 142.4 | 128.5 | 90.2 |
As can be seen from Table 2, the charging capacity of the lithium ion battery prepared from the regenerated lithium iron phosphate obtained in the example can reach 158.6mAh/g, and the initial charge and discharge efficiency can reach 94.5%.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the application, and that those skilled in the art will understand that the technical scheme of the application may be modified or equally substituted without departing from the spirit and scope of the technical scheme of the application.
Claims (15)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/087421 WO2024212075A1 (en) | 2023-04-10 | 2023-04-10 | Repair and regeneration method for lithium iron phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116723999A true CN116723999A (en) | 2023-09-08 |
| CN116723999B CN116723999B (en) | 2025-07-29 |
Family
ID=87868433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202380008814.7A Active CN116723999B (en) | 2023-04-10 | 2023-04-10 | Repairing and regenerating method of lithium iron phosphate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116723999B (en) |
| WO (1) | WO2024212075A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117401664A (en) * | 2023-11-08 | 2024-01-16 | 池州西恩新材料科技有限公司 | A dry and wet repair and regeneration method for lithium iron phosphate scraps |
| CN117819511A (en) * | 2024-01-05 | 2024-04-05 | 安徽工业大学 | A heat treatment method for recovering lithium iron phosphate waste containing a binder without oxidizing Fe(II) in the lithium iron phosphate and its application |
| CN117977038A (en) * | 2024-01-29 | 2024-05-03 | 湖南智电谷能源科技有限公司 | Method for recycling waste lithium iron phosphate battery to generate lithium manganese iron phosphate anode material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119528101A (en) * | 2024-11-11 | 2025-02-28 | 孝感楚能新能源创新科技有限公司 | A method for recycling waste lithium iron phosphate battery positive electrode material, positive electrode material, positive electrode sheet, secondary battery and power-consuming device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044503A (en) * | 2021-11-09 | 2022-02-15 | 株洲冶炼集团股份有限公司 | Method for separating, removing impurities and regenerating waste lithium iron phosphate pole pieces |
| CN114400393A (en) * | 2021-12-17 | 2022-04-26 | 中国科学院广州能源研究所 | A kind of method that utilizes heat treatment to separate positive and negative electrode powder to recover lithium iron phosphate |
| CN114784271A (en) * | 2022-04-26 | 2022-07-22 | 威尔能环保科技(苏州)有限公司 | Regenerated lithium iron phosphate positive electrode material, preparation method and application |
| CN114824544A (en) * | 2022-04-26 | 2022-07-29 | 威尔能环保科技(苏州)有限公司 | Repairing lithium iron phosphate positive electrode material, preparation method and application |
| CN115051056A (en) * | 2022-04-18 | 2022-09-13 | 福州华复新能源科技有限公司 | Method for industrially separating electrode material in process of regenerating waste electrode plate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036253B (en) * | 2019-12-09 | 2023-01-13 | 锂源(深圳)科学研究有限公司 | Method for selective oxidation-reduction regeneration of waste lithium iron phosphate, regenerated lithium iron phosphate and lithium ion battery |
| CN112234272B (en) * | 2020-09-22 | 2022-02-18 | 华中科技大学 | Low-energy-consumption and low-Al-content recovery method for lithium iron phosphate positive plate |
| CN114212765B (en) * | 2022-01-07 | 2023-06-20 | 中南大学 | A method for recycling lithium iron phosphorus components in lithium iron phosphate waste powder |
| CN114566727A (en) * | 2022-02-23 | 2022-05-31 | 株洲冶炼集团股份有限公司 | Modification method for direct pyrogenic repair and regeneration of lithium iron phosphate positive electrode material |
| CN114583313B (en) * | 2022-03-11 | 2024-02-20 | 江苏协鑫锂电科技有限公司 | A method for recycling waste phosphate cathode materials |
| CN115312897B (en) * | 2022-07-05 | 2025-07-18 | 威尔能环保科技(苏州)有限公司 | Repairing method of waste lithium iron phosphate and obtained lithium iron phosphate material |
-
2023
- 2023-04-10 WO PCT/CN2023/087421 patent/WO2024212075A1/en active Pending
- 2023-04-10 CN CN202380008814.7A patent/CN116723999B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044503A (en) * | 2021-11-09 | 2022-02-15 | 株洲冶炼集团股份有限公司 | Method for separating, removing impurities and regenerating waste lithium iron phosphate pole pieces |
| CN114400393A (en) * | 2021-12-17 | 2022-04-26 | 中国科学院广州能源研究所 | A kind of method that utilizes heat treatment to separate positive and negative electrode powder to recover lithium iron phosphate |
| CN115051056A (en) * | 2022-04-18 | 2022-09-13 | 福州华复新能源科技有限公司 | Method for industrially separating electrode material in process of regenerating waste electrode plate |
| CN114784271A (en) * | 2022-04-26 | 2022-07-22 | 威尔能环保科技(苏州)有限公司 | Regenerated lithium iron phosphate positive electrode material, preparation method and application |
| CN114824544A (en) * | 2022-04-26 | 2022-07-29 | 威尔能环保科技(苏州)有限公司 | Repairing lithium iron phosphate positive electrode material, preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117401664A (en) * | 2023-11-08 | 2024-01-16 | 池州西恩新材料科技有限公司 | A dry and wet repair and regeneration method for lithium iron phosphate scraps |
| CN117819511A (en) * | 2024-01-05 | 2024-04-05 | 安徽工业大学 | A heat treatment method for recovering lithium iron phosphate waste containing a binder without oxidizing Fe(II) in the lithium iron phosphate and its application |
| CN117977038A (en) * | 2024-01-29 | 2024-05-03 | 湖南智电谷能源科技有限公司 | Method for recycling waste lithium iron phosphate battery to generate lithium manganese iron phosphate anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116723999B (en) | 2025-07-29 |
| WO2024212075A1 (en) | 2024-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116723999B (en) | Repairing and regenerating method of lithium iron phosphate | |
| CN111392750B (en) | Method for removing impurities and recovering lithium from waste lithium ion batteries | |
| JP7220360B2 (en) | Method for recovering positive electrode material, obtained positive electrode material and use thereof | |
| JP5535717B2 (en) | Lithium recovery method | |
| CN101383441A (en) | A comprehensive recycling method for lithium iron phosphate battery positive electrode waste | |
| CN108258350A (en) | The MAT'L recycling method of waste lithium iron phosphate battery | |
| WO2024125561A1 (en) | Method for preparing carbon-coated sodium iron fluorophosphate from waste lithium iron phosphate, and use thereof | |
| CN102170036A (en) | Recycling method of lithium iron phosphate cathode materials | |
| CN104538695A (en) | Method for recycling metal in waste LiMn1-x-yNixCoyO2 battery and preparing LiMn1-x-yNixCoyO2 | |
| CN114614133A (en) | Combined treatment method for areca residue and waste cathode material | |
| CN114317968A (en) | Recycling method and application of waste lithium iron phosphate battery | |
| CN115463935A (en) | Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid wastes in metallurgical industry | |
| CN112661201A (en) | Method for preparing nickel cobalt lithium manganate through reverse positioning of power battery and application | |
| CN112047320A (en) | Treatment method for low-pollution recycling of lithium iron phosphate material | |
| CN114784271B (en) | A regenerated lithium iron phosphate positive electrode material, preparation method and application | |
| CN108172926A (en) | A kind of waste lithium ion cell anode material repair methods | |
| CN115353086A (en) | Pyrogenic recovery method for efficiently pretreating waste lithium iron phosphate cathode material | |
| CN110791668A (en) | A method for recovering manganese from manganese-containing lithium ion battery cathode waste | |
| CN103474653A (en) | Preparation method for lithium iron phosphate | |
| WO2024183014A1 (en) | Method for selectively recycling lithium and system device for selectively recycling lithium | |
| CN117185319A (en) | A method for recycling lithium iron phosphate batteries by sulfate air roasting | |
| CN115072747A (en) | Lithium carbonate recovery method and device | |
| CN119764642A (en) | A preparation method for regenerated high-nickel ternary material | |
| CN114950361B (en) | A method of preparing composite adsorbent from waste lithium batteries | |
| CN119100354A (en) | A method for preparing lithium iron phosphate positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |