CN114314691A - Impurity ion doped and regenerated ternary cathode material and preparation method and application thereof - Google Patents
Impurity ion doped and regenerated ternary cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a ternary cathode material regenerated by impurity ion doping, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) performing acid leaching and separation on the waste ternary positive electrode material to obtain primary filtrate, wherein the primary filtrate comprises active metal ions and impurity ions, and the impurity ions comprise any one or the combination of at least two of aluminum, copper, iron, calcium, magnesium, zinc, sodium, potassium or fluorine; (2) removing impurities from the primary filtrate and performing solid-liquid separation to obtain a secondary filtrate; (3) and carrying out element compounding and spray pyrolysis on the secondary filtrate to obtain a ternary oxide precursor, and sintering the ternary oxide precursor to obtain the impurity ion doped and regenerated ternary cathode material. The waste ternary cathode material is subjected to acid leaching, spray pyrolysis and sintering to prepare the impurity ion doped regenerated ternary cathode material, and the impurity ion doped regenerated ternary cathode material has the advantages of higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a ternary cathode material regenerated by impurity ion doping, and a preparation method and application thereof.
Background
The layered nickel cobalt lithium manganate ternary cathode material integrates the excellent cycle performance of lithium cobaltate, the high-capacity characteristic of lithium nickelate and the low-cost advantage of lithium manganate, has good safety performance and obvious ternary synergistic effect, and becomes a lithium ion battery cathode material with great development prospect. With the continuous improvement of the requirement on energy density, the high-nickel ternary cathode material becomes the mainstream trend of future development. However, the high nickel content increases the material structure instability while increasing the capacity of the ternary material, mainly because of Ni2+And Li+The radii are relatively close, so that cation mixing is easily caused, and side reactions at the interface of the material are caused. Doping is one of the main methods to improve cation shuffling.
CN102956882A provides a molybdenum-doped ternary material, the conductivity and the cycle performance of the material prepared by the method are greatly improved, and the rate capability and the high-temperature performance of the material are particularly improved; CN104916837A is adopted to prepare an aluminum-doped ternary positive electrode material precursor by a coprecipitation method, and then the precursor is mixed and sintered with a lithium source and a boron source, so that the physical and chemical properties of the material are improved, and the stacking density and the cycle performance of the material are improved; CN108336344A discloses a sodium ion doped high-nickel ternary lithium battery positive electrode material and a preparation method thereof, the method prepares a ternary positive electrode precursor by a coprecipitation method, then the precursor is dried and ground, mixed with powdery sodium peroxide and lithium oxide and sintered in an oxygen-rich environment to obtain the sodium ion doped high-nickel ternary lithium battery positive electrode material, the problem of mixed discharge of cations of the material is solved, and the cycle performance of the material is improved.
The problem of cation mixed discharge of the anode material is solved by doping in the prior art, but in most of the prior art, a coprecipitation method is adopted to synthesize a ternary precursor firstly, and then the doped metal salt and the lithium salt are mixed and sintered, so that the preparation method has strict requirements on parameters and complex process flow, the morphology of the prepared anode material is difficult to regulate, the improvement of the electrochemical performance of the anode material is not facilitated, and the industrial production of the anode material of the lithium ion battery is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a ternary cathode material for impurity ion doping regeneration, and a preparation method and application thereof. According to the invention, the waste ternary cathode material is subjected to acid leaching, spray pyrolysis and sintering to prepare the impurity ion doped regenerated ternary cathode material, wherein the introduction of the impurity ions and the matching of the spray pyrolysis can regulate and control the morphology and size of the material, improve the dispersion uniformity of doped elements and reduce the mixed discharge of cations; the impurity ion doped and regenerated ternary cathode material prepared by the method has the advantages of higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a ternary cathode material regenerated by impurity ion doping, which comprises the following steps:
(1) performing acid leaching and separation on a waste ternary positive electrode material to obtain primary filtrate, wherein the primary filtrate comprises active metal ions and impurity ions, and the impurity ions comprise any one or a combination of at least two of aluminum, copper, iron, calcium, magnesium, zinc, sodium, potassium or fluorine;
(2) removing impurities from the primary filtrate obtained in the step (1) and carrying out solid-liquid separation to obtain secondary filtrate;
(3) and (3) carrying out element compounding on the secondary filtrate obtained in the step (2), then carrying out spray pyrolysis to obtain a ternary oxide precursor, and sintering the ternary oxide precursor to obtain the impurity ion doped and regenerated ternary cathode material.
In the present invention, the impurity ions include any one or a combination of at least two of aluminum, copper, iron, calcium, magnesium, zinc, sodium, potassium, or fluorine, and may be, for example, a combination of copper and iron, a combination of calcium and magnesium, a combination of zinc, sodium, and potassium, a combination of sodium, potassium, and fluorine, or a combination of iron, calcium, magnesium, zinc, and sodium, or the like.
According to the invention, the waste ternary cathode material is subjected to acid leaching and separation to obtain a filtrate containing active metal ions and impurity ions, the filtrate is subjected to element doping to improve the mixed-row phenomenon of cations in the subsequent material synthesis, and then the filtrate is subjected to spray pyrolysis and sintering to prepare the impurity ion doped regenerated ternary cathode material with higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
In the prior art, metal salt is often used as a raw material, a coprecipitation method is used for preparing a metal-doped ternary precursor, and then the metal-doped ternary precursor is sintered at a high temperature to prepare a metal-doped anode material; however, the preparation method has strict requirements on parameters and a complex process flow, a large amount of alkaline wastewater is generated in the preparation process, and the prepared anode material has poor morphology, so that the electrochemical performance of the anode material is influenced.
According to the invention, the ternary precursor is prepared by selecting a spray pyrolysis mode, so that the generation process can be simplified, the production efficiency is improved, the ternary precursor can be prepared in one step, and the ternary precursor can be matched with impurity ions to regulate and control the shape and size of the material, improve the dispersion uniformity of doping elements, and further reduce the mixed discharge of cations, thereby improving the discharge capacity and coulombic efficiency of the material, and improving the rate capability and circulation stability of the material.
The source of the waste ternary cathode material is not limited, and the waste ternary cathode material containing a small amount of aluminum foil, copper foil and other impurities can be obtained by discharging, disassembling, crushing and sorting waste lithium batteries.
The preparation method disclosed by the invention is low in raw material cost and environment-friendly, ions of required elements can be obtained through one-time acid leaching, impurity ions do not need to be additionally introduced, the resource utilization of the waste battery anode material is realized, the production process is simple, the yield is high, the product quality is uniform, the repeatability is good, and the large-scale production can be realized.
Preferably, the waste ternary cathode material comprises lithium nickel cobalt manganese oxide.
Preferably, the waste ternary cathode material further comprises lithium cobaltate and/or lithium manganate.
Preferably, the active metal ions comprise lithium, nickel and cobalt, and the active metal ions further comprise manganese and/or aluminium.
Preferably, the content of the impurity ions is 0.02 to 10 wt%, for example, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, or the like, based on 100 wt% of the mass of the waste ternary cathode material, and the content of the impurity ions refers to a ratio of the mass of all the impurity ions in the waste ternary cathode material to the mass of the waste ternary cathode material before acid leaching.
As a preferable technical scheme of the preparation method, the acid leaching solution in the step (1) is a mixed solution of acid and a reducing agent.
Preferably, the acid includes any one or a combination of at least two of hydrochloric acid, nitric acid, acetic acid, oxalic acid, citric acid or malic acid, and may be, for example, a combination of hydrochloric acid and nitric acid, a combination of nitric acid and acetic acid, a combination of oxalic acid and citric acid or malic acid, or a combination of nitric acid, acetic acid, oxalic acid, citric acid and malic acid, and the like, preferably citric acid and/or hydrochloric acid.
Preferably, the concentration of the acid in the acid-leaching solution is 0.5-5 mol/L, for example, 0.5mol/L, 0.8mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 4mol/L or 5mol/L, and preferably 2-3 mol/L.
Preferably, the reducing agent comprises hydrogen peroxide.
Preferably, the content of the effective component in the reducing agent is 5 to 20 wt%, for example, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, or 20 wt%, based on 100 wt% of the acid-leached solution.
Preferably, the temperature of the acid leaching in the step (1) is 30 to 90 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃ or 90 ℃, preferably 60 to 70 ℃.
Preferably, the acid leaching time in the step (1) is 1-5 h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 4h or 5h, and the like, and preferably 2-3 h.
According to the invention, the proper acid leaching temperature and acid leaching time are selected, so that the composition types and contents of active metal ions and impurity ions in the leaching solution can be optimized, and a precursor solution with a more proper element proportion is provided for subsequent spray pyrolysis, so that the prepared material has better performance.
Preferably, the solid-to-liquid ratio of the slurry obtained by acid leaching in the step (1) is 100-500 g/L, for example, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L, 350g/L, 400g/L, 450g/L or 500g/L, and the like, and preferably 250-300 g/L.
As a preferable technical scheme of the preparation method, the impurity removal in the step (2) comprises the following steps: the pH of the primary filtrate in the step (1) is adjusted to 4-12, for example, 4, 4.5, 5, 6, 6.5, 7, 8, 9, 10, 11 or 12, and preferably 6-10.
In the prior art, the research on the preparation of the cathode material by spray pyrolysis is rare, because in the process of synthesizing metal salts of common cathode materials such as nickel, cobalt, manganese and the like by spray pyrolysis to obtain a cathode material precursor, although the synthesis process is simplified, the rate performance of the cathode material is improved to a certain extent, the particles of the cathode material precursor are irregular, and hollow or broken particles are easily generated, so that the tap density of the prepared cathode material is far lower than that of the material prepared by a coprecipitation method, and the method is a main factor for preventing the spray pyrolysis technology from realizing industrial application in the field of the cathode material of the lithium ion battery.
According to the invention, a waste ternary cathode material with low cost is used as a raw material, impurity elements Al, Cu, Fe, Ca, Mg, Zn, Na, K or F contained in the waste ternary cathode material are used as doping ions, the pH value of filtrate and the concentration of the impurity ions in the filtrate are adjusted through the precise regulation and control of a preorder impurity removal process, the type and content of the doping elements are optimized, the problem of cation mixed discharge of the cathode material is remarkably improved, the particle morphology and size of the material are further regulated and controlled through an additive, and therefore, the electrochemical performance of the material is improved; at the preferred pH and/or impurity ion concentration of the present invention, the material has higher discharge capacity, better coulombic efficiency, longer cycle life and better cycle stability.
Preferably, the manner of adjusting the pH is by adding a pH buffer.
Preferably, the pH buffer comprises ammonia.
Preferably, in the secondary filtrate of step (2), the total content of impurity ions is 0.01 to 5 wt%, for example, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 1 wt%, 2 wt%, or 5 wt%, and more preferably 0.01 to 2 wt%, based on 100 wt% of the solute in the secondary filtrate.
As a preferred technical scheme of the preparation method, the element compounding in the step (3) comprises the following steps: and mixing the secondary filtrate with metal salt to obtain mixed feed liquid.
Preferably, the metal salt includes any one or a combination of at least two of lithium salt, nickel salt, cobalt salt or manganese salt, for example, the combination may be a combination of lithium salt and nickel salt, a combination of nickel salt and cobalt salt, a combination of nickel salt, cobalt salt and manganese salt, or a combination of lithium salt, nickel salt, cobalt salt and manganese salt, and the like, and the proportion of active metal ions in the mixed solution is adjusted by additionally adding metal salt to the secondary filtrate, so as to obtain the specific type of positive electrode material.
Preferably, the ratio Li (Ni + Co + Mn) of the amount of the substance of lithium ions to the amount of the total substance of nickel ions, cobalt ions and manganese ions in the mixed feed liquid is (1-1.1): 1, and may be, for example, 1:1, 1.01:1, 1.02:1, 1.05:1, 1.06:1, 1.08:1, 1.1:1, or the like.
In a specific embodiment, the mass ratio of nickel ions, cobalt ions and manganese ions in the mixed feed liquid, Ni: Co: Mn, is 1:1:1, 5:2:3, 6:2:2 or 8:1:1, preferably 8:1: 1. Preferably, the lithium salt includes any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium oxalate and lithium acetate, and may be, for example, a combination of lithium hydroxide and lithium carbonate, a combination of lithium carbonate and lithium oxalate, a combination of lithium carbonate, lithium oxalate and lithium acetate, or a combination of lithium hydroxide, lithium carbonate, lithium oxalate and lithium acetate, and the like, and preferably lithium carbonate.
Preferably, the nickel salt includes any one or a combination of at least two of nickel chloride, nickel nitrate or nickel acetate, and may be, for example, a combination of nickel chloride and nickel nitrate, a combination of nickel nitrate and nickel acetate, or a combination of nickel chloride, nickel nitrate and nickel acetate, and the like, preferably nickel chloride.
Preferably, the cobalt salt includes any one of cobalt chloride, cobalt nitrate or cobalt acetate or a combination of at least two of them, and may be, for example, a combination of cobalt chloride and cobalt nitrate, a combination of cobalt nitrate and cobalt acetate, or a combination of cobalt chloride, cobalt nitrate and cobalt acetate, etc., preferably cobalt chloride.
Preferably, the manganese salt comprises any one or a combination of at least two of manganese chloride, manganese nitrate or manganese acetate, for example, a combination of manganese chloride and manganese nitrate, a combination of manganese nitrate and manganese acetate, a combination of manganese chloride, manganese nitrate and manganese acetate, and the like, preferably manganese chloride.
As a preferred technical scheme of the preparation method, after the element is compounded in the step (3) and before the spray pyrolysis, the secondary filtrate after the element is compounded is mixed with a carbon source and a dispersing agent.
According to the invention, two additives, namely the carbon source and the dispersing agent, are added into the secondary filtrate, so that the dispersibility of the doped elements in the subsequent spray pyrolysis process can be improved, the appearance and the size of the ternary precursor obtained by spray pyrolysis can be improved, and the high-performance high-tap-density cathode material can be obtained.
Preferably, the carbon source comprises glucose and/or sucrose, preferably glucose.
Preferably, the mass fraction of the carbon source is 1 to 10 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, preferably 5 to 8 wt%, based on 100 wt% of the solute in the secondary filtrate after the re-compounding.
Preferably, the dispersant comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol, polyacrylamide or cetyl trimethyl ammonium bromide, and may be, for example, a combination of polyethylene glycol and polyvinyl alcohol, a combination of polyvinyl alcohol and polyacrylamide, or a combination of polyvinyl alcohol, polyacrylamide and cetyl trimethyl ammonium bromide, etc., preferably polyethylene glycol.
Preferably, the mass fraction of the dispersant is 0.1 to 5 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, and preferably 1 to 2 wt%, based on 100 wt% of the solute in the secondary filtrate after the compounding.
The carbon source and the dispersing agent with proper types and contents can be used for obtaining a better dispersing effect, and the stability of the anode material is further improved by matching with spray pyrolysis.
In a preferred embodiment of the preparation method of the present invention, the temperature of the spray pyrolysis in step (3) is 300 to 800 ℃, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, or 800 ℃, preferably 400 to 500 ℃.
Preferably, the time of the spray pyrolysis in the step (3) is 1 to 10s, for example, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, and the like, and preferably 2 to 5 s.
Preferably, the sintering temperature in the step (3) is 600-900 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, preferably 750-800 ℃.
Preferably, the sintering time in the step (3) is 5-15 h, for example, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, preferably 8-10 h.
Preferably, the sintering protective gas in step (3) is any one or a combination of at least two of nitrogen, argon or helium, and may be, for example, a combination of nitrogen and argon, a combination of argon and helium, a combination of nitrogen, argon and helium, or the like, preferably nitrogen.
In a second aspect, the invention provides a ternary cathode material regenerated by doping impurity ions, which is prepared by the preparation method of the first aspect.
The impurity ion doped and regenerated ternary cathode material has the advantages of higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
Preferably, the chemical formula of the impurity ion doping regenerated ternary cathode material is LiaNixCoyM1-x-yNbO2Wherein a is more than or equal to 1 and less than or equal to 1.2 and 0<x<1，0<y<1，0<x+y<B is more than or equal to 1, 0.001 and less than or equal to 0.1, M comprises Mn and/or Al, N comprises any one or the combination of at least two of Al, Cu, Fe, Ca, Mg, Zn, Na, K or F.
In the present invention, 1. ltoreq. a.ltoreq.1.2, for example, 1, 1.01, 1.02, 1.05, 1.08, 1.1, 1.15, 1.2 or the like, 0< x <1, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 or the like, 0< y <1, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 or the like, 0< x + y <1, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 or the like, 0.001. ltoreq. b.ltoreq.0.1, for example, 0.005, 0.01, 0.02, 0.06, 0.05, 0.09, 0.07, or the like.
In the present invention, N includes any one or a combination of at least two of Al, Cu, Fe, Ca, Mg, Zn, Na, K, or F, and may be, for example, a combination of Al and Cu, a combination of Fe and Ca, a combination of Ca, Mg, and Zn, or a combination of Mg, Zn, Na, K, and F.
Preferably, 0.6 ≦ x < 1.
In a third aspect, the invention provides a lithium ion battery, and a positive electrode of the lithium ion battery comprises the ternary positive electrode material regenerated by impurity ion doping according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects: (1) according to the invention, the waste ternary cathode material is subjected to acid leaching, spray pyrolysis and sintering to prepare the impurity ion doped regenerated ternary cathode material, wherein the introduction of the impurity ions and the matching of the spray pyrolysis can regulate and control the morphology and size of the material, improve the dispersion uniformity of doped elements and reduce the mixed discharge of cations; the impurity ion doped and regenerated ternary cathode material prepared by the method has the advantages of higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
(2) The preparation method disclosed by the invention is low in raw material cost and environment-friendly, ions of required elements can be obtained through one-time acid leaching, impurity ions do not need to be additionally introduced, the resource utilization of the waste battery anode material is realized, the production process is simple, the yield is high, the product quality is uniform, the repeatability is good, and the large-scale production can be realized.
Drawings
Fig. 1 is a process flow chart of preparing a ternary cathode material regenerated by impurity ion doping in an embodiment of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The embodiment of the invention partially provides a preparation method of a ternary cathode material regenerated by impurity ion doping, a process flow chart is shown in figure 1, and the preparation method comprises the following steps:
(1) performing acid leaching and separation on a waste ternary positive electrode material to obtain primary filtrate, wherein the primary filtrate comprises active metal ions and impurity ions, and the impurity ions comprise any one or a combination of at least two of aluminum, copper, iron, calcium, magnesium, zinc, sodium, potassium or fluorine;
(2) removing impurities from the primary filtrate obtained in the step (1) and carrying out solid-liquid separation to obtain secondary filtrate;
(3) and (3) carrying out element compounding on the secondary filtrate obtained in the step (2), then carrying out spray pyrolysis to obtain a ternary oxide precursor, and sintering the ternary oxide precursor to obtain the impurity ion doped and regenerated ternary cathode material.
According to the invention, the ternary precursor is prepared by selecting a spray pyrolysis mode, so that the generation process can be simplified, the production efficiency is improved, the ternary precursor can be prepared in one step, and the ternary precursor can be matched with impurity ions to regulate and control the shape and size of the material, improve the dispersion uniformity of doping elements, and further reduce the mixed discharge of cations, thereby improving the discharge capacity and coulombic efficiency of the material, and improving the rate capability and circulation stability of the material.
The waste ternary cathode material is subjected to acid leaching reaction to obtain primary filtrate and filter residue, the filter residue is removed, the obtained primary filtrate can be leached circularly, the use amount of acid can be saved, and metal ions in the waste ternary cathode material can be further leached.
In some embodiments, the waste ternary positive electrode material is waste ternary material black powder.
In some embodiments, the spent ternary positive electrode material comprises lithium nickel cobalt manganese oxide.
In some embodiments, the waste ternary positive electrode material further comprises lithium cobaltate and/or lithium manganate.
In some embodiments, the active metal ions include lithium, nickel, and cobalt, and the active metal ions further include manganese and/or aluminum.
In some embodiments, the content of the impurity ions is 0.02 to 10 wt% based on 100 wt% of the mass of the waste ternary cathode material.
In some embodiments, the acid leaching solution of step (1) is a mixed solution of an acid and a reducing agent.
In some embodiments, the acid comprises any one of hydrochloric acid, nitric acid, acetic acid, oxalic acid, citric acid, or malic acid, or a combination of at least two thereof, preferably citric acid and/or hydrochloric acid.
In some embodiments, the concentration of the acid in the acid leaching solution is 0.5-5 mol/L, preferably 2-3 mol/L.
In some embodiments, the reducing agent comprises hydrogen peroxide.
In some embodiments, the content of the effective component in the reducing agent is 5 to 20 wt% based on 100 wt% of the acid-leached solution.
In some embodiments, the solid-to-liquid ratio of the slurry obtained by acid leaching in step (1) is 100-500 g/L.
In some embodiments, the solid-to-liquid ratio of the slurry obtained by acid leaching in step (1) is 250-300 g/L.
In some embodiments, the temperature of the acid leaching in step (1) is 30 to 90 ℃, preferably 60 to 70 ℃.
In some embodiments, the acid leaching time in step (1) is 1 to 5 hours, preferably 2 to 3 hours.
In some embodiments, the removing of impurities in step (2) comprises: adjusting the pH value of the primary filtrate obtained in the step (1) to 4-12, preferably 6-10, and removing filter residues in the filtrate again after adjusting the pH value.
In some embodiments, the secondary filtrate in the step (2) contains impurity ions in a total amount of 0.01 to 5 wt% based on 100% by mass of solute in the secondary filtrate.
In some embodiments, the secondary filtrate in the step (2) contains impurity ions in a total amount of 0.01 to 2 wt% based on 100% by mass of solute in the secondary filtrate.
In some embodiments, the means for adjusting the pH is the addition of a pH buffer.
In some embodiments, the pH buffer is aqueous ammonia.
In some embodiments, the elemental compounding of step (3) comprises: and mixing the secondary filtrate with metal salt to obtain mixed feed liquid.
In some embodiments, the metal salt comprises any one of a lithium salt, a nickel salt, a cobalt salt, or a manganese salt, or a combination of at least two thereof.
In some embodiments, the ratio Li (Ni + Co + Mn) of the amount of lithium ions to the total amount of nickel ions, cobalt ions and manganese ions in the mixed feed liquid is (1-1.1): 1.
In some embodiments, the lithium salt comprises any one of lithium hydroxide, lithium carbonate, lithium oxalate, or lithium acetate, or a combination of at least two thereof, preferably lithium carbonate.
In some embodiments, the nickel salt comprises any one of nickel chloride, nickel nitrate, or nickel acetate, or a combination of at least two thereof, preferably nickel chloride.
In some embodiments, the cobalt salt comprises any one of cobalt chloride, nitric acid, or cobalt acetate, or a combination of at least two thereof, preferably cobalt chloride.
In some embodiments, the manganese salt comprises any one of manganese chloride, manganese nitrate, or manganese acetate, or a combination of at least two thereof, preferably manganese chloride.
In some embodiments, after the element is compounded in the step (3) and before the spray pyrolysis, the secondary filtrate after the element is compounded is further mixed with a carbon source and a dispersing agent, the carbon source and the dispersing agent are additives, and the process of adding the additives and the metal salt is an element compounding process.
In some embodiments, the carbon source comprises glucose and/or sucrose, preferably glucose.
In some embodiments, the mass fraction of the carbon source is 1 to 10 wt%, preferably 5 to 8 wt%, based on 100 wt% of the solute in the secondary filtrate after the compounding.
In some embodiments, the dispersant comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol, polyacrylamide, or cetyltrimethylammonium bromide, preferably polyethylene glycol.
In some embodiments, the mass fraction of the dispersant is 0.1-5 wt%, preferably 1-2 wt%, based on 100 wt% of the solute in the secondary filtrate after the compounding.
In some embodiments, the temperature of the spray pyrolysis in step (3) is 300 to 800 ℃, preferably 400 to 500 ℃.
In some embodiments, the time for the spray pyrolysis in step (3) is 1 to 10 seconds, preferably 2 to 5 seconds.
In some embodiments, the sintering temperature in step (3) is 600-900 ℃, preferably 750-800 ℃.
In some embodiments, the sintering time in step (3) is 5 to 15 hours, preferably 8 to 10 hours.
In some embodiments, the sintering protective gas in step (3) is any one or a combination of at least two of nitrogen, argon or helium, preferably nitrogen.
Example 1
The mass contents of the elements in the waste ternary cathode material used in this example are shown in table 1, and the mass contents of the elements are calculated by taking the mass of the waste ternary cathode material as 100 wt%.
TABLE 1
| Element(s) | Li | Ni | Co | Mn | Al | Zn | Cu |
| Content (wt%) | 7.5 | 36 | 12.0 | 11.2 | 0.8 | 0.4 | 0.6 |
The embodiment provides a ternary cathode material regenerated by impurity ion doping and a preparation method thereof, wherein the chemical formula of the ternary cathode material regenerated by impurity ion doping is Li1.05Ni0.6Co0.2Mn0.2Al0.015Zn0.005Cu0.005O2The preparation method comprises the following steps:
(1) adding a waste ternary positive electrode material containing nickel cobalt lithium manganate into water, stirring and mixing to obtain slurry, wherein the total content of impurity ions in the waste ternary positive electrode material is 1.8 wt%, adding 2.5mol/L hydrochloric acid and 10 wt% hydrogen peroxide, adjusting the solid-to-liquid ratio of the slurry to be 250g/L, reacting at 70 ℃ for 3 hours, carrying out solid-liquid separation after the reaction is finished to obtain primary filtrate, wherein the filtrate contains ions of lithium, nickel, cobalt, manganese, aluminum, copper and zinc, and the leaching rate of each metal in the waste ternary positive electrode material is more than 98%;
(2) adding ammonia water into the primary filtrate obtained in the step (1), adjusting the pH value to 6, then carrying out solid-liquid separation to remove part of aluminum and copper ions, reducing the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after the solid-liquid separation to about 1 wt%, supplementing and adding lithium carbonate, nickel chloride, cobalt chloride and manganese chloride to obtain a mixed feed liquid, and regulating the mass ratio Li (Ni + Co + Mn) in the mixed feed liquid to be 1.05: 1;
(3) and (3) adding 5 wt% of glucose and 2 wt% of polyethylene glycol into the mixed material liquid obtained in the step (2) by taking the mass of the solute in the mixed material liquid as 100 wt%, mixing, performing spray pyrolysis at the temperature of 450 ℃ for 4s to obtain a ternary precursor, and sintering the ternary precursor at the temperature of 800 ℃ for 10h in a nitrogen atmosphere to obtain the impurity ion doped and regenerated ternary cathode material.
Example 2
The embodiment provides a ternary cathode material regenerated by impurity ion doping and a preparation method thereof, and the chemistry of the ternary cathode material regenerated by impurity ion dopingIs represented by the formula Li1.06Ni0.6Co0.2Mn0.2Al0.015Zn0.005Cu0.005O2The preparation method comprises the following steps:
(1) adding a waste ternary positive electrode material containing nickel cobalt lithium manganate into water, stirring and mixing to obtain slurry, wherein the total content of impurity ions in the waste ternary positive electrode material is 1.8 wt%, adding 3mol/L hydrochloric acid and 8 wt% hydrogen peroxide, adjusting the solid-to-liquid ratio of the slurry to 300g/L, reacting at 65 ℃ for 3 hours, and performing solid-liquid separation after the reaction is finished to obtain primary filtrate, wherein the filtrate contains ions of lithium, nickel, cobalt, manganese, aluminum, copper and zinc, and the leaching rate of each metal in the waste ternary positive electrode material is more than 98%;
(2) adding ammonia water into the primary filtrate obtained in the step (1), adjusting the pH value to 6, then carrying out solid-liquid separation to remove part of aluminum and copper ions, reducing the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after the solid-liquid separation to about 1 wt%, supplementing and adding lithium carbonate, nickel nitrate, cobalt chloride and manganese chloride to obtain a mixed feed liquid, and regulating the mass ratio Li (Ni + Co + Mn) in the mixed feed liquid to be 1.06: 1;
(3) and (3) adding 8 wt% of glucose and 1.5 wt% of polyethylene glycol into the mixed material liquid obtained in the step (2) by taking the mass of the solute in the mixed material liquid as 100 wt%, mixing, performing spray pyrolysis at the temperature of 400 ℃ for 5s to obtain a ternary precursor, and sintering the ternary precursor at the temperature of 800 ℃ for 8h in a nitrogen atmosphere to obtain the impurity ion doped and regenerated ternary cathode material.
The used ternary cathode material used in this example was the same as in example 1.
Example 3
The embodiment provides a ternary cathode material regenerated by impurity ion doping and a preparation method thereof, wherein the chemical formula of the ternary cathode material regenerated by impurity ion doping is Li1.04Ni0.6Co0.2Mn0.2Al0.015Zn0.005Cu0.005O2The preparation method comprises the following steps:
(1) adding a waste ternary positive electrode material containing nickel cobalt lithium manganate into water, stirring and mixing to obtain slurry, wherein the total content of impurity ions in the waste ternary positive electrode material is 1.8 wt%, adding 2mol/L hydrochloric acid and 15 wt% hydrogen peroxide, adjusting the solid-to-liquid ratio of the slurry to be 250g/L, reacting at 70 ℃ for 2 hours, and performing solid-liquid separation after the reaction is finished to obtain primary filtrate, wherein the filtrate contains ions of lithium, nickel, cobalt, manganese, aluminum, copper and zinc, and the leaching rate of each metal in the waste ternary positive electrode material is more than 98%;
(2) adding ammonia water into the primary filtrate obtained in the step (1), adjusting the pH value to 6, then carrying out solid-liquid separation to remove part of aluminum and copper ions, reducing the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after the solid-liquid separation to about 1 wt%, supplementing and adding lithium carbonate, nickel chloride, cobalt nitrate and manganese chloride to obtain a mixed feed liquid, and regulating the mass ratio Li (Ni + Co + Mn) in the mixed feed liquid to be 1.04: 1;
(3) and (3) adding 6 wt% of glucose and 1.2 wt% of polyvinyl alcohol into the mixed material liquid obtained in the step (2) by taking the mass of the solute in the mixed material liquid as 100 wt%, mixing, performing spray pyrolysis at the temperature of 500 ℃ for 3s to obtain a ternary precursor, and sintering the ternary precursor at the temperature of 750 ℃ for 10h in a nitrogen atmosphere to obtain the impurity ion doped and regenerated ternary cathode material.
The used ternary cathode material used in this example was the same as in example 1.
Example 4
The embodiment provides a ternary cathode material regenerated by impurity ion doping and a preparation method thereof, wherein the chemical formula of the ternary cathode material regenerated by impurity ion doping is Li1.05Ni0.6Co0.2Mn0.2Al0.01Zn0.005Cu0.005O2The preparation method comprises the following steps:
the process is the same as that of example 1 except that the pH value is adjusted to 8 in step (2), most of aluminum and copper ions are removed, and the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after solid-liquid separation is reduced to about 0.9 wt%.
Example 5
The embodiment provides a ternary cathode material for impurity ion doping regeneration and a method for preparing the sameThe chemical formula of the impurity ion doped regenerated ternary cathode material is Li1.05Ni0.6Co0.2Mn0.2Al0.006Zn0.005Cu0.004O2The preparation method comprises the following steps:
the process is the same as example 1 except that the pH value is adjusted to 10 in step (2), most of aluminum and copper ions are removed, and the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after solid-liquid separation is reduced to about 0.8 wt%.
Example 6
The embodiment provides a ternary cathode material regenerated by impurity ion doping and a preparation method thereof, wherein the chemical formula of the ternary cathode material regenerated by impurity ion doping is Li1.0Ni0.6Co0.2Mn0.2Al0.02Zn0.006Cu0.009O2The preparation method comprises the following steps:
the process is the same as example 1 except that the pH value is adjusted to 3 in step (2), the effect of removing impurity ions is not obvious, and the total content of impurity ions Al, Zn and Cu in the secondary filtrate obtained after solid-liquid separation is about 1.7 wt%.
Example 7
The procedure of example 1 was repeated except that no polyethylene glycol was added in the step (3).
Example 8
The same procedure as in example 1 was repeated except that the temperature of the spray pyrolysis in step (3) was 300 ℃.
Example 9
The procedure of example 1 was repeated except that the temperature of the spray pyrolysis in step (3) was 700 ℃.
Comparative example 1
The procedure of example 1 was repeated except that, without conducting the operations of steps (1) and (2), lithium carbonate, nickel chloride, cobalt chloride and manganese chloride were directly mixed in the solution in such a manner that the ratio of the amounts of substances, Li (Ni + Co + Mn), was 1.05: 1.
Comparative example 2
This comparative example provides a commercial conventional commercial nickel-cobalt-manganese ternary positive electrode material (NCM 622-S760).
The impurity ion doped and regenerated ternary cathode materials of examples 1-9 and comparative examples 1-2, a conductive agent Super P and a binder PVDF are mixed according to a mass ratio of 8:1:1, and dissolved in N-methyl pyrrolidone (NMP) to prepare cathode slurry, the cathode slurry is laid on an aluminum foil, dried, cut into pieces to serve as a cathode, a metal lithium piece to serve as a cathode, a polyethylene film to serve as a diaphragm, and a solute of electrolyte is 1M LiPF6The solvent is a mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1:1, and the CR2016 button lithium ion battery is assembled by sequentially stacking and compressing a negative electrode shell, a negative electrode, electrolyte, a diaphragm, the electrolyte, a positive electrode, a current collector and a positive electrode shell.
And (3) carrying out electrochemical performance test on the prepared lithium ion battery, wherein the test voltage is 3.0-4.3V, the nominal specific capacity is 1C-200 mAh/g, the first discharge capacity and the first coulombic efficiency are tested at 0.1C, and the cycle life of the battery is tested at 1C, namely the cycle frequency when the battery capacity is attenuated to 80% of the initial capacity. The test results are shown in table 2.
TABLE 2
| Sample (I) | First discharge capacity (mAh/g) | First coulombic efficiency (%) | Cycle life (times) |
| Example 1 | 195 | 90 | 1000 |
| Example 2 | 193 | 87 | 1000 |
| Example 3 | 188 | 86 | 900 |
| Example 4 | 190 | 87 | 850 |
| Example 5 | 192 | 85 | 800 |
| Example 6 | 183 | 87 | 700 |
| Example 7 | 186 | 88 | 600 |
| Example 8 | 183 | 85 | 550 |
| Example 9 | 185 | 87 | 600 |
| Comparative example 1 | 160 | 75 | 300 |
| Comparative example 2 | 175 | 85 | 500 |
As can be seen from the above examples 1 to 9, the regenerated ternary positive electrode material doped with impurity ions is prepared by performing acid leaching, spray pyrolysis and sintering on the waste ternary positive electrode material, wherein the introduction of the impurity ions and the matching of the spray pyrolysis can regulate the morphology and size of the material, improve the dispersion uniformity of the doped elements, and reduce the mixed discharge of cations; the impurity ion doped and regenerated ternary cathode material prepared by the method has the advantages of higher discharge capacity, better coulombic efficiency, longer cycle life and good cycle stability.
As can be seen from the comparison between the example 1 and the examples 4 to 6, the electrochemical performance of the ternary cathode material regenerated by doping the impurity ions can be improved by adjusting the pH value of the filtrate and the concentration of the impurity ions in the invention; when the pH value of the filtrate is higher and the concentration of impurity ions is lower, the content of doped ions in the anode material is lower, the effect of improving cation mixing is weakened, and the cycling stability of the battery is reduced; when the pH value of the filtrate is low and the concentration of impurity ions is high, the content of doped ions in the anode material is too high, the specific capacity of the battery is reduced, and the cycling stability is reduced; therefore, at a suitable pH and concentration of impurity ions, the overall performance of the material is optimal.
As can be seen from the comparison between the embodiment 1 and the embodiment 7, the dispersing agent is added in the preparation process of the invention, so that the dispersing effect of the doping elements can be improved, the morphology of the material can be regulated, and the electrochemical performance of the material can be improved together with the cooperation of spray pyrolysis; example 7 does not contain a dispersant, so that the prepared material has a high degree of agglomeration in the subsequent spray pyrolysis process, so that the specific capacity and the cycling stability of example 7 are inferior to those of example 1.
It can be known from comparison between example 1 and examples 8 to 9 that the invention selects a suitable spray pyrolysis temperature to cooperate with impurity ions to prepare the impurity ion doped regenerated ternary cathode material, which can better improve the electrochemical performance of the material, when the spray pyrolysis temperature is higher, the volatilization speed of the solvent in the pyrolysis process is too fast, the particles of the formed oxide material are larger, and when the spray pyrolysis temperature is lower, the oxidation of the chlorinated metal salt is insufficient, and the content of chloride radicals in the formed oxide material is higher, so that the overall battery performance of example 1 is higher than that of examples 8 to 9.
The comparison between the embodiment 1 and the comparative examples 1-2 shows that the preparation method for providing multiple doping elements by using the waste ternary cathode material can improve the electrochemical performance of the prepared impurity ion doped regenerated ternary cathode material, multiple metal salts are directly mixed in the comparative example 1, the phenomenon that impurity ions cooperate with spray pyrolysis to regulate the morphology of the material and inhibit mixed cation discharge is avoided, the comparative example 2 is an industrial commercial material prepared by a coprecipitation method, the particle size of the material is larger, and the performances of the cathode material prepared by the two methods are inferior to those of the embodiment 1.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The preparation method of the impurity ion doped regenerated ternary cathode material is characterized by comprising the following steps of:
(1) performing acid leaching and separation on a waste ternary positive electrode material to obtain primary filtrate, wherein the primary filtrate comprises active metal ions and impurity ions, and the impurity ions comprise any one or a combination of at least two of aluminum, copper, iron, calcium, magnesium, zinc, sodium, potassium or fluorine;
(2) removing impurities from the primary filtrate obtained in the step (1) and carrying out solid-liquid separation to obtain secondary filtrate;
(3) and (3) carrying out element compounding on the secondary filtrate obtained in the step (2), then carrying out spray pyrolysis to obtain a ternary oxide precursor, and sintering the ternary oxide precursor to obtain the impurity ion doped and regenerated ternary cathode material.
2. The preparation method according to claim 1, wherein the waste ternary positive electrode material comprises lithium nickel cobalt manganese oxide;
preferably, the waste ternary cathode material further comprises lithium cobaltate and/or lithium manganate;
preferably, the active metal ions comprise lithium, nickel and cobalt, and the active metal ions further comprise manganese and/or aluminum;
preferably, the content of the impurity ions is 0.02-10 wt% based on 100 wt% of the waste ternary cathode material.
3. The production method according to claim 1 or 2, wherein the acid-leaching solution of step (1) is a mixed solution of an acid and a reducing agent;
preferably, the acid comprises any one or a combination of at least two of hydrochloric acid, nitric acid, acetic acid, oxalic acid, citric acid or malic acid, preferably citric acid and/or hydrochloric acid;
preferably, in the acid leaching solution, the concentration of acid is 0.5-5 mol/L, preferably 2-3 mol/L;
preferably, the reducing agent comprises hydrogen peroxide;
preferably, the content of the effective components in the reducing agent is 5-20 wt% based on 100 wt% of the acid leaching solution;
preferably, the solid-to-liquid ratio of the slurry obtained by acid leaching in the step (1) is 100-500 g/L, and preferably 250-300 g/L;
preferably, the acid leaching time in the step (1) is 1-5 h, preferably 2-3 h;
preferably, the acid leaching temperature in the step (1) is 30-90 ℃, and preferably 60-70 ℃.
4. The method according to any one of claims 1 to 3, wherein the removing of the impurities in the step (2) comprises: adjusting the pH of the primary filtrate obtained in the step (1) to 4-12, preferably 6-10;
preferably, the manner of adjusting the pH is to add a pH buffer;
preferably, the pH buffer comprises ammonia;
preferably, in the secondary filtrate in the step (2), the total content of impurity ions is 0.01 to 5 wt%, and more preferably 0.01 to 2 wt%, based on 100% of the mass of solute in the secondary filtrate.
5. The method according to any one of claims 1 to 4, wherein the element compounding in step (3) comprises: mixing the secondary filtrate with metal salt to obtain mixed feed liquid;
preferably, the metal salt comprises any one of lithium salt, nickel salt, cobalt salt or manganese salt or a combination of at least two of the salts;
preferably, the ratio Li (Ni + Co + Mn) of the amount of lithium ions in the mixed feed liquid to the total amount of nickel ions, cobalt ions and manganese ions is (1-1.1): 1;
preferably, the lithium salt comprises any one of lithium hydroxide, lithium carbonate, lithium oxalate or lithium acetate or a combination of at least two of the foregoing, preferably lithium carbonate;
preferably, the nickel salt comprises any one of nickel chloride, nickel nitrate or nickel acetate or a combination of at least two of the nickel chloride, the nickel nitrate or the nickel acetate is preferably nickel chloride;
preferably, the cobalt salt comprises any one of cobalt chloride, cobalt nitrate or cobalt acetate or a combination of at least two of them, preferably cobalt chloride;
preferably, the manganese salt comprises any one of manganese chloride, manganese nitrate or manganese acetate or a combination of at least two of them, preferably manganese chloride.
6. The preparation method according to any one of claims 1 to 5, wherein after the element compounding in the step (3) and before the spray pyrolysis, the secondary filtrate after the element compounding is further mixed with a carbon source and a dispersant;
preferably, the carbon source comprises glucose and/or sucrose, preferably glucose;
preferably, the mass fraction of the carbon source is 1-10 wt%, preferably 5-8 wt%, based on 100 wt% of solute in the compounded secondary filtrate;
preferably, the dispersant comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol, polyacrylamide or cetyl trimethyl ammonium bromide, preferably polyethylene glycol;
preferably, the mass fraction of the dispersant is 0.1-5 wt%, preferably 1-2 wt%, calculated by the mass of the solute in the secondary filtrate after compounding being 100 wt%.
7. The method according to any one of claims 1 to 6, wherein the temperature of the spray pyrolysis in the step (3) is 300 to 800 ℃, preferably 400 to 500 ℃;
preferably, the time of the spray pyrolysis in the step (3) is 1-10 s, preferably 2-5 s;
preferably, the sintering temperature in the step (3) is 600-900 ℃, and preferably 750-800 ℃;
preferably, the sintering time in the step (3) is 5-15 h, preferably 8-10 h;
preferably, the sintering protective gas in step (3) is any one or a combination of at least two of nitrogen, argon or helium, preferably nitrogen.
8. The impurity ion doped and regenerated ternary cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The impurity ion doping regenerated ternary cathode material according to claim 8, wherein the chemical formula of the impurity ion doping regenerated ternary cathode material is LiaNixCoyM1-x-yNbO2Wherein a is more than or equal to 1 and less than or equal to 1.2 and 0<x<1，0<y<1，0<x+y<B is more than or equal to 1, 0.001 and less than or equal to 0.1, M comprises Mn and/or Al, N comprises any one or the combination of at least two of Al, Cu, Fe, Ca, Mg, Zn, Na, K or F;
preferably, 0.6 ≦ x < 1.
10. A lithium ion battery, characterized in that the ternary cathode material regenerated by impurity ion doping according to claim 8 or 9 is included in a cathode of the lithium ion battery.
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