CN112978808A - Layered oxide positive electrode material of lithium, preparation and application - Google Patents
Layered oxide positive electrode material of lithium, preparation and application Download PDFInfo
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a method for preparing a layered oxide cathode material of lithium, belonging to the field of resource recycling. The method uses the raw material of the layered oxide anode material of the waste lithium ion battery, and is characterized by comprising the following steps: firstly, analyzing the valence state of metal elements and the proportion of each metal element in the waste layered oxide anode material by ICP (inductively coupled plasma) and XPS (XPS), and adjusting the valence state of the metal elements and the proportion of each metal element in the waste layered oxide anode material by utilizing metal salt with redox characteristics through a certain reaction to realize the regeneration of the anode material. The method directly utilizes the waste layered oxide anode material separated from the waste lithium ion battery to regenerate and prepare the layered oxide anode material which can be practically applied, and has the advantages of simple process, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials and waste battery recycling, and particularly relates to a method for preparing a transition metal layered oxide anode material of lithium.
Background
The lithium ion battery realizes industrial and commercial application in the early 90 s of the 20 th century, has the advantages of high voltage, high specific energy, long cycle life, no memory effect and the like, greatly improves the safety, and is widely applied to the fields of portable equipment such as mobile communication, notebook computers and the like, electric automobiles, large-scale energy storage and the like. According to statistics, the lithium ion battery market yield in 2018 reaches 102.00GWH, and is predicted to reach 205.33GWH in 2020. The service life of the lithium ion battery, particularly the power lithium ion battery, is generally 3-5 years, and the recycling of the waste battery can form a huge market. The proportion of the positive electrode material in the waste battery is about 40-50%.
The lithium metal layered oxide anode material has the advantages of high specific capacity, good cycle performance and the like, and the usage amount of the lithium metal layered oxide anode material in the lithium ion battery anode material is increased year by year. The waste layered oxide positive electrode material contains valuable metals such as lithium, nickel, cobalt, manganese and the like, environmental pollution and resource waste can be caused due to improper treatment, and the reasonable recycling of the metal elements can effectively save resources, thereby having important significance for environmental protection and economic sustainable development.
The main recovery technology of the waste Lithium Ion battery is introduced in a Recycling End-of-Life Electric Vehicle Lithium-Ion Batteries [ J ] (Joule,2019) system of Chen M, Ma X, Chen B, et al, and mainly comprises a pyrometallurgical process, a hydrometallurgical process and a direct recovery and regeneration process. The pyrometallurgical process adopts an ultrahigh-temperature method to treat the waste lithium ion battery, converts the waste lithium ion battery into metal alloy (containing metals such as nickel, cobalt, manganese and the like), and combines a hydrometallurgical process to prepare a new anode material. A large amount of energy is consumed and a large amount of tail gas is generated in the pyrometallurgical recovery process, a tail gas treatment device is needed, the recovery cost is high, and the recovery rate is low. The hydrometallurgy process adopts acid or alkali leaching, and then separation and purification are carried out to realize the recovery of the anode material. CN108306071A discloses a waste lithium ion battery anode material recovery process, which comprises the steps of carrying out acid leaching on waste anode materials to convert the waste anode materials into metal ions, and then carrying out a coprecipitation process to synthesize an anode material again; the whole recovery process has complex process and more flows, generates a large amount of waste water, increases the pollution treatment cost and is easy to cause secondary pollution. The direct recovery process is to directly recover and regenerate the anode material on the basis of keeping the structure of the original material. The direct recovery and regeneration process is simple, the pollution emission is less, and the regenerated material can be directly used. CN110364748 discloses a method for regenerating a waste lithium ion battery anode material, which comprises the steps of carrying out high-temperature calcination on the waste anode material and excessive lithium-containing compounds to obtain a regenerated anode material; although the process flow is simplified, the change of the valence states of metal ions such as nickel, manganese and the like in the waste anode material is not considered, and the structural change of the material cannot be fundamentally recovered. After the layered oxide cathode material is used, the element proportions of lithium, nickel, cobalt and manganese and the valence of transition metals of nickel, cobalt and manganese are changed. The difficulty of directly recycling and regenerating the waste layered oxide anode material is the adjustment of the valence state of the transition metal in the recycling process. Therefore, despite the great progress made in the recovery technology of the waste lithium ion batteries in recent years, there is no method for directly preparing the positive electrode material by adjusting the valence state of the metal in the waste layered oxide positive electrode material.
Disclosure of Invention
The invention aims to provide a regeneration method of a layered oxide anode material of a waste lithium ion battery, which has the advantages of simple process, low cost and small environmental pollution. The method directly utilizes the waste layered oxide anode material separated from the waste lithium ion battery, utilizes metal salt with redox characteristics, and adjusts the valence state of metal elements and the proportion of each metal element in the waste layered oxide anode material through a certain reaction, thereby realizing the regeneration of the waste lithium ion battery layered oxide anode material.
In order to achieve the above object, the present invention provides a method for preparing a layered oxide positive electrode material of lithium, comprising the steps of: step (1), a layered oxide positive electrode material recovered from a waste lithium ion battery is subjected to measurement and analysis of the valence state of each metal element in the layered oxide positive electrode material by using an photoelectron spectrometer XPS, and the molar ratio of each metal element in the layered oxide positive electrode material is subjected to measurement and analysis by using an element analyzer ICP; calculating the types and the molar weight of metals to be supplemented according to the molar ratio of each element in the initial layered oxide anode material of the battery and the total weight of the waste layered oxide anode material;
step (2), calculating the addition amount of metal salt with redox characteristics according to the molar amount of metal to be supplemented; calculating whether the requirement of recovering the valence state of other metal elements except lithium in the cathode material to the amount of the redox agent required by the target cathode material is met or not according to the anions and the cations introduced by the addition amount of the metal salt; whether the valence state of other metal elements except lithium in the recovered positive electrode material is larger than or equal to the amount of the corresponding valence state in the target positive electrode material, and if the valence state is smaller than the amount of the corresponding valence state, the metal salt with the redox property of all the metals is supplemented at the same time according to the molar proportion of all the metals in the target positive electrode material; the anion introduced into the metal salt has oxidizability, and if the metal is introduced into the metal salt, a low-valence metal ion Co is adopted2+、Mn2+、Mn3+One or more of them have reducibility; step (3), uniformly mixing the waste anode material and the supplemented metal salt solution, and adjusting the proportion of each element in the waste anode material and the valence state of each metal element by adopting a certain synthesis method to obtain a primary anode material I;
and (4) uniformly mixing the primary positive electrode material I and a lithium salt according to a certain ratio Li/M (Li is lithium in the lithium salt, and M is other metals except the lithium in the primary positive electrode material I), and performing segmented high-temperature roasting under the condition of air and/or oxygen to obtain a regenerated positive electrode material, wherein the lithium salt is used for supplementing the loss of the lithium in the high-temperature roasting process.
In the above-described aspect, the metal salt having redox properties is one or more of sulfate, nitrate, chlorate and acetate of a metal contained in the target positive electrode material;
in the technical scheme, the synthesis method can be one or two or three combined applications of a solvothermal method, a spray pyrolysis method or a vapor deposition method;
the solvothermal method has the reaction temperature of 100-300 ℃, preferably 150-200 ℃; the reaction time is 2 to 48 hours, preferably 5 to 12 hours;
the spray pyrolysis method has the pyrolysis temperature of 300-900 ℃, preferably 400-600 ℃; the reaction time is 2 to 48 hours, preferably 2 to 10 hours;
the vapor deposition method has the reaction temperature of 300-900 ℃, preferably 300-600 ℃; the reaction time is 0.1-12h, preferably 1-5 h.
In the above technical scheme, the concentration of the metal salt solution is 0.01-10mol/L, preferably 0.02-5 mol/L.
In the above technical solution, the lithium salt may be one or more than two of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, and lithium oxalate.
In the technical scheme, the Li/M is 0.1-30%, preferably 1-10%.
In the technical scheme, the step-by-step high-temperature roasting is carried out by firstly carrying out heat preservation for 2-8h at the temperature of 600 ℃ under the temperature of 300-; preferably, the temperature is 400 ℃ and 550 ℃ for 3-6h, and the temperature is 700 ℃ and 900 ℃ for 10-18 h.
In the technical scheme, the initial material is a layered oxide anode material adopted in the preparation of the waste lithium ion battery;
the layered oxide cathode material adopted during preparation or the layered oxide cathode material (namely the target cathode material) for preparing the lithium ion battery comprises any one or more than two of the following materials
LiCoO, a unitary layered material2，LiNiO2，LiMnO2One or more than two of them;
binary layered material LiNixCo1-xO2(where 0 < x < 1), LiNixMn1-xO2(where 0 < x < 1), LiCoxMn1-xO2(wherein 0 < x < 1);
ternary layered material LiNixCoyMzO2(wherein x is 0 < 1, y is 0 < 1, and 0 <z < 1, x + y + z ═ 1, M can be Mn or Al); doping modified ternary material LiNixCoyMnzM1-x-y-zO2(wherein x + y + z is less than 1, x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, M can be one or more than two of Na, Al, Mg, Cr, Zr, Ti, Fe, Zn, La and Mo);
lithium-rich manganese-based material xLi2MnO3·(1-x)LiMO2(wherein x is more than 0 and less than 1, and M is one or more of Ni, Co and Mn). In the technical scheme, the regenerated layered oxide material is used as a positive electrode material and applied to a lithium ion battery.
Compared with the prior art, the technical scheme of the invention can realize the regeneration of the layered oxide anode material by utilizing the metal salt with redox property to adjust the valence state of the metal elements and the proportion of each metal element in the waste layered oxide anode material on the basis of keeping the original material. According to the method, acid leaching is avoided, pollutants such as waste gas and waste liquid are reduced, the process flow of recycling the waste layered oxide anode material is shortened, and efficient recycling of the waste layered oxide anode material is realized.
Drawings
FIG. 1 is a first-cycle charge-discharge curve diagram of the regenerated positive electrode material prepared in example 1 of the present invention
FIG. 2 is a first-turn charge-discharge curve diagram of the regenerated cathode material prepared in example 2 of the present invention
FIG. 3 is a first-cycle charge-discharge curve diagram of the regenerated cathode material prepared in example 3 of the present invention
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples:
example 1
And (3) recovering the anode material from the waste lithium ion battery, wherein the initial anode material is NCM 111. ICP (inductively coupled plasma) measurement is adopted to analyze the molar ratio of metal elements Li, Ni, Co and Mn in the waste positive electrode material to be 0.96:0.33:0.33:0.31, XPS (XPS) measurement is adopted to analyze the valence of Ni, Co and Mn in the waste positive electrode material, wherein 20% of Ni appears in the Ni element3+Out of Mn elementNow 30% Mn3+. 100g of waste anode material, 5.8g of manganese nitrate and 3.4g of lithium nitrate are weighed according to the molar ratio of Li, Ni, Co and Mn of 1:0.33:0.33:0.33 to prepare a solution, and the concentration of metal ions is 0.1 mol/L. The added material can be Ni3+Reduction to Ni2+，Mn3+By oxidation to Mn4+Therefore, the metal salt does not need to be added secondarily. And uniformly mixing the metal salt solution and the waste anode material, and introducing the mixture into a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the reaction temperature of 160 ℃ for 8 hours. And after the reaction is finished, filtering, washing and drying the precipitate to obtain a primary cathode material I. 3.7g of lithium hydroxide is weighed and uniformly mixed with the primary cathode material I, and Li/(Ni + Co + Mn) in the lithium hydroxide is 5%. And (3) roasting the mixture at high temperature in sections, preserving heat for 5h at 450 ℃, preserving heat for 12h at 900 ℃, and naturally cooling to obtain the repaired and regenerated layered oxide cathode material.
The regenerated positive electrode material obtained in the embodiment is assembled into a CR2016 type button cell by using the regenerated positive electrode material as a positive active material, a metal lithium sheet as a negative electrode, and lithium hexafluorophosphate as an electrolyte, and a charge-discharge test is performed on a blue test system at 0.1C, so that the first-loop specific discharge capacity is 156.0mAh/g, and the capacity retention rate is 94.8% after 100 cycles of charge-discharge cycle. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Example 2
And recovering a positive electrode material from the waste lithium ion battery, wherein the initial positive electrode material is NCM 811. ICP (inductively coupled plasma) measurement is adopted to analyze the molar ratio of metal elements Li, Ni, Co and Mn in the waste positive electrode material to be 0.95:0.78:0.10:0.08, XPS (XPS) measurement is adopted to analyze the valence of Ni, Co and Mn in the waste positive electrode material, wherein the Ni element contains 40% of Ni3+The Mn element contains 20% of Mn3+. 100g of waste anode material, 8.4g of nickel sulfate, 3.8g of manganese sulfate and 6.0g of lithium perchlorate are weighed according to the molar ratio of Li to Ni to Co to Mn of 1:0.8:0.1:0.1 to prepare a solution. The added material cannot mix Ni with3+Is completely reduced into Ni2+Therefore, secondary addition of metal salts is required. Weighing 1.1g of lithium perchlorate, 2.1g of nickel sulfate, 0.3g of cobalt sulfate and 0.2g of manganese sulfate according to the molar ratio of Li to Ni to Co to Mn of 1:0.8:0.1:0.1And uniformly mixing the solution with metal ions with the concentration of 0.2mol/L, uniformly mixing the metal salt solution and the waste anode material, introducing the mixture into a reactor for spray pyrolysis reaction at the reaction temperature of 400 ℃ for 5 hours, and obtaining a primary anode material I. 1.1g of lithium carbonate is weighed and uniformly mixed with the primary cathode material I, wherein Li/(Ni + Co + Mn) in the lithium carbonate is 0.1%. And (3) roasting the mixture at high temperature in sections, preserving heat for 6h at 400 ℃, preserving heat for 12h at 800 ℃, and naturally cooling to obtain the repaired and regenerated layered oxide cathode material.
The regenerated positive electrode material obtained in the embodiment is assembled into a CR2016 type button cell by using the regenerated positive electrode material as a positive active material, a metal lithium sheet as a negative electrode, and lithium hexafluorophosphate as an electrolyte, and a charge-discharge test is performed on a blue test system at 0.1C, wherein the first-cycle specific discharge capacity is 196.1mAh/g, and the capacity retention rate is 93.5% after 100 cycles of charge-discharge cycle. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Example 3
Recovering the anode material from the waste lithium ion battery, wherein the initial anode material is 0.5Li2MnO3·0.5LiNi0.4Co0.3Mn0.3O2. ICP (inductively coupled plasma) measurement is adopted to analyze the molar ratio of Li to Ni to Co to Mn in the waste positive electrode material is 1.35:0.20:0.15:0.60, XPS (XPS) measurement is adopted to analyze the valence of Ni to Co to Mn in the waste positive electrode material, wherein the Mn element contains 25% of Mn3+. Weighing 100g of waste anode material and 16.4g of manganese perchlorate and 7.5g of lithium acetate to prepare a solution according to the molar ratio of Li, Ni, Co and Mn of 1.50:0.20:0.15:0.65, wherein the added material can be Mn3+By oxidation to Mn4+Therefore, the metal salt does not need to be added secondarily. And uniformly mixing the metal salt solution and the waste anode material, and introducing the mixture into a reactor for vapor deposition reaction at the reaction temperature of 500 ℃ for 2 hours to obtain a primary anode material I. 10.5g of lithium acetate is weighed and uniformly mixed with the primary cathode material I, wherein Li/(Ni + Co + Mn) in the lithium acetate is 10%. The mixture is roasted at high temperature in sections, the temperature is kept at 450 ℃ for 6h, the temperature is kept at 850 ℃ for 12h, and the mixture is naturally cooled to obtain the repaired and regenerated layered oxideA pole material.
The regenerated positive electrode material obtained in the embodiment is assembled into a CR2016 type button cell by using the regenerated positive electrode material as a positive active material, a metal lithium sheet as a negative electrode, and lithium hexafluorophosphate as an electrolyte, and a charge-discharge test is performed on a blue test system at 0.1C, wherein the first discharge specific capacity is 255.8mAh/g, and the capacity retention rate is 91.3% after 100 cycles of charge-discharge cycle. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Example 4
Recovering positive electrode material from waste lithium ion battery, wherein the initial positive electrode material is LiNi0.6Co0.2Mn0.16Mg0.04O2,. Analyzing the molar ratio of metal elements Li, Ni, Co, Mn and Mg in the waste cathode material by ICP (inductively coupled plasma) measurement of 0.96:0.78:0.20:0.16:0.04, and analyzing the valence of Ni, Co and Mn in the waste cathode material by XPS (XPS) measurement, wherein the Ni element contains 20 percent of Ni3+The Mn element contains 20% of Mn3+. Weighing 7.8g of nickel acetate and 5.0 g of lithium acetate to prepare a solution according to the molar ratio of Li, Ni, Co and Mn of 1:0.6:0.2:0.16, wherein the added material can be Ni3+Reduction to Ni2+，Mn3+By oxidation to Mn4+Therefore, the metal salt does not need to be added secondarily. The concentration of metal ions in the solution is 0.1mol/L, the metal salt solution and the waste anode material are uniformly mixed, and the mixture is introduced into a reactor to carry out spray pyrolysis reaction at the reaction temperature of 400 ℃ for 5 hours to obtain a primary anode material I. 4.0g of lithium carbonate is weighed and uniformly mixed with the primary cathode material I, wherein Li/(Ni + Co + Mn + Mg) in the lithium carbonate is 5%. And (3) roasting the mixture at high temperature in sections, preserving heat for 5h at 500 ℃, preserving heat for 12h at 850 ℃, and naturally cooling to obtain the repaired and regenerated layered oxide cathode material.
The regenerated positive electrode material obtained in the embodiment is assembled into a CR2016 type button cell by using the regenerated positive electrode material as a positive active material, a metal lithium sheet as a negative electrode, and lithium hexafluorophosphate as an electrolyte, and a charge-discharge test is performed on a blue test system at 0.1C, so that the first discharge specific capacity is 178.4mAh/g, and the capacity retention rate is 92.6% after 100 cycles of charge-discharge cycle. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Example 5
Recovering positive electrode material from waste lithium ion battery, wherein the initial positive electrode material is LiNi0.8Mn0.2O2. ICP (inductively coupled plasma) measurement is used for analyzing the molar ratio of metal elements Li to Ni to Mn (0.96: 0.78: 0.22), XPS (XPS) measurement is used for analyzing the valence of Ni to Mn in the waste cathode material, wherein part of 50% of Ni appears in the Ni element3+. According to the mol ratio of Li, Ni and Mn of 1:0.8: 0.2. 100g of waste cathode material is weighed, and 10.5g of nickel nitrate and 6.8g of lithium nitrate are weighed to prepare a solution. The added material cannot mix Ni with3+Is completely reduced into Ni2+Therefore, secondary addition of metal salts is required. According to the molar ratio of Li to Ni to Mn of 1:0.8:0.2, 0.4g of lithium nitrate, 1.2g of nickel nitrate and 0.4g of manganese nitrate are weighed and mixed with the solution uniformly. The concentration of metal ions in the solution is 0.3mol/L, the metal salt solution and the waste anode material are uniformly mixed, and the mixture is introduced into a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the temperature of 160 ℃ for 8 hours. And after the reaction is finished, filtering, washing and drying the precipitate to obtain a primary cathode material I. 10g of lithium nitrate is weighed and uniformly mixed with the primary cathode material I, and Li/(Ni + Mn) in the lithium nitrate is 30%. And (3) roasting the mixture at high temperature in sections, preserving heat for 5h at 500 ℃, preserving heat for 12h at 800 ℃, and naturally cooling to obtain the repaired and regenerated layered oxide cathode material.
The regenerated cathode material obtained in the embodiment is subjected to charge and discharge tests at 0.1C, the first circle of discharge specific capacity is 185.4mAh/g, and after 100 cycles of charge and discharge, the capacity retention rate is 90.3%. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Example 6
Recovering anode material from waste lithium ion battery, wherein the initial anode material is LiCoO2. ICP (inductively coupled plasma) measurement and analysis are carried out on the molar ratio of metal elements Li to Co in the waste positive electrode material to be 0.91:1, XPS (XPS) measurement and analysis are carried out on the valence of Co in the waste positive electrode material, wherein Co is mainly used as Co element3+The adjustment of the valence state of the metal is not required. According to the mol ratio of Li to Co of 1:1,0.09mol of metallic lithium is added for each mol of cobalt. Weighing 100g of waste anode material, weighing 6.3g of lithium nitrate to prepare a solution, wherein the concentration of metal ions in the solution is 0.5mol/L, uniformly mixing the lithium salt solution and the waste anode material, and introducing the mixture into a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the reaction temperature of 180 ℃ for 10 hours. And after the reaction is finished, filtering, washing and drying the precipitate to obtain a primary cathode material I. 9.5g of lithium oxalate was weighed out together with the primary positive electrode material I, the Li/Co ratio in the lithium oxalate being 10%. And (3) roasting the mixture at high temperature in sections, preserving heat for 5h at 500 ℃, preserving heat for 12h at 800 ℃, and naturally cooling to obtain the repaired and regenerated layered oxide cathode material.
The regenerated positive electrode material obtained in the embodiment is assembled into a CR2016 type button cell by using the regenerated positive electrode material as a positive active material, a metal lithium sheet as a negative electrode, and lithium hexafluorophosphate as an electrolyte, and a charge-discharge test is performed on a blue test system at 0.1C, wherein the first discharge specific capacity is 181.5mAh/g, and the capacity retention rate is 93.7% after 100 cycles of charge-discharge cycle. The regenerated cathode material can be directly used as a cathode material of a lithium ion battery.
Claims (10)
1. A method for preparing a layered oxide positive electrode material of lithium is characterized in that: the method uses a raw material which is a layered oxide anode material separated from the waste lithium ion battery, utilizes metal salt with redox characteristics to adjust the valence state and the element proportion of metal elements in the waste layered oxide anode material through chemical reaction, and returns the valence state and the element proportion of an initial material or prepares the layered oxide anode material of the lithium ion battery, namely a target anode material, so as to realize the regeneration of the layered oxide anode material of the waste lithium ion battery; the metal salt with redox property is one or more of sulfate, nitrate, chlorate and acetate of metal contained in the target positive electrode material;
the preparation process comprises the following steps:
step (1), a layered oxide positive electrode material recovered from a waste lithium ion battery is subjected to measurement and analysis of the valence state of each metal element in the layered oxide positive electrode material by using an photoelectron spectrometer XPS, and the molar ratio of each metal element in the layered oxide positive electrode material is subjected to measurement and analysis by using an element analyzer ICP; calculating the types and the molar weight of metals to be supplemented according to the molar ratio of each element in the initial layered oxide anode material of the battery and the total weight of the waste layered oxide anode material;
step (2), calculating the addition amount of metal salt with redox characteristics according to the molar amount of metal to be supplemented; calculating whether the requirement of recovering the valence state of other metal elements except lithium in the cathode material to the amount of the redox agent required by the target cathode material is met or not according to the anions and the cations introduced by the addition amount of the metal salt; whether the valence state of other metal elements except lithium in the recovered positive electrode material is larger than or equal to the amount of the corresponding valence state in the target positive electrode material, and if the valence state is smaller than the amount of the corresponding valence state, the metal salt with the redox property of all the metals is supplemented at the same time according to the molar proportion of all the metals in the target positive electrode material; the anion introduced into the metal salt has oxidizability, and if the metal is introduced into the metal salt, a low-valence metal ion Co is adopted2+、Mn2+、Mn3+One or more of them have reducibility;
step (3), uniformly mixing the waste anode material and the supplemented metal salt solution, and adjusting the proportion of each metal element and the valence state of each metal element in the waste anode material by adopting a certain synthesis method to obtain a primary anode material I;
and (4) uniformly mixing the primary positive electrode material I and a lithium salt according to a certain ratio Li/M (Li is lithium in the lithium salt, and M is other metals except the lithium in the primary positive electrode material I), and performing segmented high-temperature roasting under the condition of air and/or oxygen to obtain a regenerated positive electrode material, wherein the lithium salt is used for supplementing the loss of the lithium in the high-temperature roasting process.
2. The method of claim 1, wherein: the synthesis method in the step (3) can be one or two or three of a solvent thermal method, a spray pyrolysis method or a vapor deposition method;
the solvothermal method has the reaction temperature of 100-300 ℃, preferably 150-200 ℃; the reaction time is 2 to 48 hours, preferably 5 to 12 hours;
the spray pyrolysis method has the pyrolysis temperature of 300-900 ℃, preferably 400-600 ℃; the reaction time is 2 to 48 hours, preferably 2 to 10 hours;
the vapor deposition method has the reaction temperature of 300-900 ℃, preferably 300-600 ℃; the reaction time is 0.1-12h, preferably 1-5 h.
3. The method of claim 1, wherein: the concentration of the solution of the metal salt in the step (3) is 0.01 to 10mol/L, preferably 0.02 to 5 mol/L.
4. The method of claim 1, wherein: wherein the lithium salt in the step (4) can be one or more than two of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and lithium oxalate.
5. The method of claim 1, wherein: wherein the Li/M ratio in the step (4) is 0.1-30%, preferably 1-10%.
6. The method of claim 1, wherein: wherein the step (4) of high-temperature roasting is carried out by firstly preserving heat for 2-8h at the temperature of 600 ℃ under 300-; preferably, the temperature is 400 ℃ and 550 ℃ for 3-6h, and the temperature is 700 ℃ and 900 ℃ for 10-18 h.
7. The method of claim 1,
the initial material is a layered oxide anode material adopted in the preparation of the waste lithium ion battery;
the layered oxide cathode material adopted during preparation or the layered oxide cathode material (namely the target cathode material) for preparing the lithium ion battery comprises any one or more than two of the following materials
LiCoO, a unitary layered material2，LiNiO2，LiMnO2One or more than two of them;
binary layerLiNi materialxCo1-xO2(where 0 < x < 1), LiNixMn1-xO2(where 0 < x < 1), LiCoxMn1-xO2(wherein 0 < x < 1);
ternary layered material LiNixCoyMzO2(wherein 0 < x < 1, 0 < y < 1, 0 < z < 1, x + y + z ═ 1, and M can be Mn or Al);
doping modified ternary material LiNixCoyMnzM1-x-y-zO2(wherein x + y + z is less than 1, x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, M can be one or more than two of Na, Al, Mg, Cr, Zr, Ti, Fe, Zn, La and Mo);
lithium-rich manganese-based material xLi2MnO3·(1-x)LiMO2(wherein x is more than 0 and less than 1, and M is one or more of Ni, Co and Mn).
8. A regenerated positive electrode material prepared by the method of any one of claims 1 to 7.
9. Use of the positive electrode material according to claim 8, wherein the regenerated layered oxide material is used as a positive electrode material in a lithium ion battery.
10. Use of a positive electrode material according to claim 9, characterized in that the specific capacity of the regenerated positive electrode material is not less than 80% of the starting material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113636605A (en) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | Physical repair method for completely-failed ternary positive electrode material under low-cost air condition |
| CN115432741A (en) * | 2022-09-23 | 2022-12-06 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for recycling waste lithium battery positive plate and battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103296269A (en) * | 2013-05-17 | 2013-09-11 | 太原理工大学 | Green controllable preparation process of lithium nickel cobalt manganese oxide |
| CN103915661A (en) * | 2013-01-09 | 2014-07-09 | 中国科学院过程工程研究所 | Method for direct recovery and restoration of lithium ion battery positive electrode material |
| CN108447698A (en) * | 2018-03-12 | 2018-08-24 | 中国科学院长春应用化学研究所 | A kind of electrode and preparation method thereof, the renewable storing up electricity device of high energy |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915661A (en) * | 2013-01-09 | 2014-07-09 | 中国科学院过程工程研究所 | Method for direct recovery and restoration of lithium ion battery positive electrode material |
| CN103296269A (en) * | 2013-05-17 | 2013-09-11 | 太原理工大学 | Green controllable preparation process of lithium nickel cobalt manganese oxide |
| CN108447698A (en) * | 2018-03-12 | 2018-08-24 | 中国科学院长春应用化学研究所 | A kind of electrode and preparation method thereof, the renewable storing up electricity device of high energy |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636605A (en) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | Physical repair method for completely-failed ternary positive electrode material under low-cost air condition |
| CN115432741A (en) * | 2022-09-23 | 2022-12-06 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for recycling waste lithium battery positive plate and battery |
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