CN109088115B - Method for preparing ternary cathode material by recycling waste lithium ion battery cathode material - Google Patents
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Abstract
the invention discloses a method for preparing a ternary cathode material by recycling a waste lithium ion battery cathode material, which belongs to the field of recycling of non-ferrous metal secondary resources, wherein lithium is extracted firstly, and then a precursor is prepared, so that L i during preparation of the precursor by using a waste leachate is eliminated +Influence on morphology and crystal form: the waste positive electrode material is subjected to alkaline leaching, reduction roasting and lithium extraction, then is leached by inorganic acid, and after impurity removal, the leaching solution is prepared into a nickel-cobalt-manganese salt solution according to the product requirement, and then is subjected to coprecipitation to prepare a precursor. The method comprises the steps of preliminarily forming a cathode material by a hydrothermal method under the conditions of low lithium consumption and low liquid-solid ratio, directly drying, grinding and uniformly mixing hydrothermal products without filtering and cleaning, and roasting by one step to obtain the ternary cathode material which is full in lithium intercalation, good in crystal form, free of agglomeration and excellent in electrochemical performance. The method organically combines the recovery of the waste battery materials with the preparation of the anode material, is suitable for treating various battery anode wastes, and has the advantages of wide raw material sources, short process, simple equipment and excellent performance of the prepared nickel-cobalt-manganese ternary anode material.
Description
Technical Field
The invention relates to the recycling of non-ferrous metal secondary resources, in particular to a method for recycling and preparing a ternary cathode material from a cathode material in a waste lithium ion battery.
Background
In recent years, lithium ion batteries are widely used as secondary energy sources in electric vehicles, unmanned aerial vehicles, mobile intelligent terminals such as mobile phones, tablet computers and notebook computers. With the rapid development of the application market in the global scope, the output of the lithium ion batteries also increases rapidly, and meanwhile, a large amount of waste lithium ion batteries flow to the society, so that resources in the waste lithium ion batteries are urgently needed to be recycled and potential environmental pollution is avoided.
The lithium ion battery anode material mainly comprises lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt aluminate, ternary lithium nickel cobalt aluminate and the like in the past and at present, and contains abundant valuable metals such as lithium, nickel, cobalt, manganese, aluminum and the like. Under the new situation of advocating development of circular economy and green and efficient utilization of secondary resources, high-valued recycling becomes a new trend of treating the waste lithium ion batteries at present, so that development of a new process method for organically combining resource recycling of the waste lithium ion batteries and new material synthesis is urgently needed.
in the aspect of recycling, different types of anode materials are difficult to classify when the waste lithium ion batteries are recycled, waste anodes obtained after disassembly and separation often contain multiple anode materials, and valuable metals such as L i, Ni, Co, Mn and the like and impurities such as Cu, Fe, Al, Ca, Mg and the like are also contained in subsequent leachate +difficult to remove prior to co-precipitation, resulting in L i +The crystal form and the appearance of the precursor are seriously influenced, so that the performance of the subsequent anode material is influenced.
In the aspect of synthesis, the nickel-cobalt-manganese ternary cathode material is widely applied due to the characteristics of low cost, high capacity and the like, and the main components of the nickel-cobalt-manganese waste cathode material are consistent with those of the ternary cathode material, so that the nickel-cobalt-manganese ternary cathode material is an ideal recycled product. Coprecipitation-roasting is the mainstream commercial production method, and the precursor Ni containing nickel, cobalt and manganese obtained by coprecipitation xCoyMn1-x-y(OH)2Or N ixCoyMn1-x- yCO3and L i 2CO3or L iOH. H 2And the lithium sources such as O and the like are obtained by two-stage roasting. Although the coprecipitation-baking method is commercially successful, the baking process usually requires pre-baking at 450-550 ℃ for more than 5 hours Roasting at 750-950 ℃ for more than 10h, wherein the long-time roasting brings obvious defects: high energy consumption, serious lithium volatilization loss, poor crystal form and serious agglomeration of the obtained anode material, and influence on the yield and the electrochemical performance of the anode material.
The hydrothermal method is mainly used for the aspects of precursor preparation, positive electrode material modification and the like in the field of positive electrode material preparation; the hydrothermal method is usually carried out in a closed container, the raw materials and the aqueous solution are heated to more than 100 ℃, and the material which can be synthesized only at high temperature is prepared at low temperature under the self-pressure or external pressure.
The patent CN101355161A discloses a method for preparing lithium nickel cobalt manganese oxide as a positive electrode material of a lithium ion battery, which adopts the technical scheme that a manganese compound, a nickel compound, lithium cobaltate and lithium hydroxide are used as raw materials, a precursor is obtained by filtering, washing and drying after hydrothermal treatment, lithium hydroxide is added into the precursor, and the mixture is mixed and roasted for the first time to obtain a ternary positive electrode material. Although the method utilizes hydrothermal synthesis and simplifies the roasting process, the consumption of lithium in the process is large;
Patent CN105428639A discloses a hydrothermal synthesis method using nickel-cobalt-manganese hydroxide as a raw material, wherein the nickel-cobalt-manganese hydroxide is mixed with a lithium source, then ozone is introduced for oxidation, and a subsequent hydrothermal reaction product is roasted to obtain a ternary cathode material. The method avoids the condition of uneven mixing of nickel, cobalt and manganese on raw materials, but still does not avoid the problem of large using amount of lithium hydroxide.
In summary, the prior art for recycling and preparing the anode material of the waste lithium ion battery mainly has the following defects: the influence of lithium during coprecipitation and the lithium loss caused by the complicated subsequent roasting process flow cannot be eliminated, and the product is easy to agglomerate; the technical disadvantages of the hydrothermal synthesis of the ternary cathode material mainly include large lithium consumption, complex process and the like, and particularly, the production cost is undoubtedly increased when the price of the lithium raw material rises.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing a precursor by taking a nickel-cobalt-manganese waste lithium ion battery as a raw material and then performing hydrothermal synthesis under low lithium consumption firstly adopting reduction roasting-carbonated water to extract lithium and eliminating L i when preparing precursor by subsequent coprecipitation +the prepared precursor is mixed with a lithium source for hydrothermal synthesis, the lithium-embedded ternary material is obtained by adopting low lithium dosage and low liquid-solid ratio, the hydrothermal product is directly dried without solid-liquid separation, the L i loss caused by a filtration and cleaning process and the process is avoided, and the product which is free of agglomeration, good in crystal form and excellent in electrochemical performance can be obtained by grinding and simple roasting after drying.
The purpose of the invention is realized by the following technical scheme:
A method for preparing a ternary cathode material by recycling a waste lithium ion battery cathode material comprises the following steps:
Step one, alkaline leaching aluminum removal: adding alkali liquor into the positive electrode waste to leach aluminum, filtering to obtain alkaline leaching residues and alkaline leaching solution, drying the alkaline leaching residues, and separately recovering aluminum from the alkaline leaching solution;
Step two, roasting/extracting lithium: mixing and roasting the alkali leaching residue and a reducing agent, leaching with water while introducing carbon dioxide to extract lithium, filtering to obtain a lithium-rich solution and filter residue, and evaporating and crystallizing the lithium-rich solution to obtain a lithium-containing product;
Step three, acid leaching: adding acid into the filter residue obtained in the second step for leaching, filtering to obtain a leaching solution and acid leaching residue, and recovering carbon from the acid leaching residue;
Step four, impurity removal: adding a vulcanizing agent into the pickle liquor to remove Fe and Cu, adding villiaumite to remove Ca and Mg, and finally removing aluminum by hydrolysis to obtain a solution after impurity removal;
step five, preparing a liquid mixture, namely detecting the concentration of nickel, cobalt and manganese in the liquid after impurity removal, adding soluble nickel salt, cobalt salt or manganese salt according to the proportion of nickel, cobalt and manganese components in a target product, and adding water to enable the concentration of total metal ions of nickel, cobalt and manganese to be 0.5-2.5 mol/L;
Step six, coprecipitation: slowly adding the solution obtained in the fifth step, a sodium hydroxide solution and dilute ammonia water into a stirring reactor under a protective atmosphere for coprecipitation, and filtering to obtain a precursor Ni xCoyMn1-x-y(OH)2；
step seven, hydro-thermal synthesis, namely adding a precursor, a lithium source, an additive and water into a high-pressure reaction kettle, wherein the additive is one or a mixture of hydrogen peroxide, oxygen and ozone, the dosage of lithium is L i/(Ni + Co + Mn) in a molar ratio of 1.0-1.07, the dosage of the additive is O/(Ni + Co + Mn) in a molar ratio of 0.1-10, preferably 0.4-4, and the liquid-solid ratio L/S is 1: 1-4: 1, preferably 1: 1-2: 1;
Step eight, drying/mixing: directly drying the hydrothermal product without solid-liquid separation, and drying the product by ball milling and mixing;
Step nine, roasting: and roasting the mixed materials at the temperature of 750-900 ℃ for 2-10 hours to obtain the anode material, wherein the roasting temperature is preferably 800-850 ℃, and the roasting time is preferably 4-5 hours.
Further, the positive electrode waste material treated in the step one is one or a mixture of more of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganate, lithium nickel cobalt aluminate and lithium-rich manganese-based solid solution.
Further, the reducing agent used in the second step is a solid reducing agent of lignite, bituminous coal, anthracite or a gaseous reducing agent of CO and H 2The sum of the mass of C and H in the reducing agent is 4-20% of the mass of the anode waste, the roasting temperature is 400-700 ℃, and the roasting time is 0.5-4H; the liquid-solid ratio is 1: 1-10: 1 during water immersion, and CO is introduced 2The molar weight of the lithium-containing solid is 0.55-10 times of that of lithium in the solid, and the leaching time is 0.5-3 hours.
further, in the third step, the acid is one of sulfuric acid, nitric acid or hydrochloric acid, the liquid-solid ratio is 2: 1-20: 1, the concentration is 1-2.5 mol/L, and the acid leaching temperature is 20-90 ℃.
further, the concentration of the sodium hydroxide used in the sixth step is 0.5-2.5 mol/L, the concentration of the dilute ammonia water is 0.2-1.0 mol/L, the protective gas is one or a mixed gas of nitrogen or argon, the reaction temperature is 40-70 ℃, and the reaction time is 5-20 hours.
Further, in the seventh step, the precursor is fresh dry material or wet material; the hydrothermal temperature is 140-250 ℃, and the heat preservation time is 1-6 h.
Further, directly drying the hydrothermal product in the step eight, wherein the drying temperature is 80-120 ℃, and the drying time is 2-10 hours.
According to the technical scheme provided by the invention, the implementation of the method is mainly characterized in that the precursor preparation is performed by extracting lithium firstly and then coprecipitating, the lithium dosage is low during hydrothermal synthesis, solid-liquid separation is avoided, most of lithium is inserted into the precursor in the process, a ternary material is preliminarily formed, and a product which is free of agglomeration, good in crystal form and excellent in electrochemical performance can be obtained by roasting for a period of time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic flow chart of the present invention;
FIG. 2 is a graph of charge-discharge cycle performance at 1C for the ternary cathode material prepared in EXAMPLE 1;
Fig. 3 is an electron microscope image of the ternary cathode material prepared in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
200g of nickel-cobalt-manganese lithium ion battery positive electrode waste is crushed, ground and subjected to alkaline leaching, alkaline leaching residues are dried and then mixed with lignite, the mass of carbon in the lignite is 10% of that of the alkaline leaching residues, and the lignite is placed in a muffle furnace for roasting at the temperature of 600 ℃ for 3 hours. Placing the roasted product in water, stirring and introducing CO 2When the mixture is immersed in water, the liquid-solid ratio is 3:1, and CO is introduced 2The molar weight of the lithium-enriched solution is 2 times of the molar weight of the lithium in the solid, the time is 1.5h, and the lithium-enriched solution is obtained by filtration. Filtering residue adding into 3L sulfuric acid solution with concentration of 2 mol/L, stirring at constant temperature of 60 deg.C for 3 hr, filtering to obtain sulfate solution containing Co, Ni and Mn, and adding Na into the acid leaching solution, wherein the recovery rate of each valuable element is 92.3% of Li, 99.0% of Co, 98.0% of Ni and 99.2% of Mn 2S, removing Fe and Cu, adding NaF to remove Ca and Mg, and finally removing aluminum by hydrolysis to obtain impurity-removed liquid, wherein the components are shown in Table 1:
| Ni | Co | Mn | Cu | Fe | Al | Ca | Mg |
| 10.5g/L | 18.8g/L | 9.8g/L | <0.1ppm | <2.0ppm | <1.0ppm | <2.0ppm | <1.0ppm |
TABLE 1 post-purification Nickel cobalt manganese sulfate solution composition
preparing solutions according to the equimolar amount of nickel, cobalt and manganese, respectively adding 105.4g of cobalt sulfate heptahydrate, 209.0g of nickel sulfate hexahydrate and 136.7g of manganese sulfate monohydrate into the purified sulfate solution, dissolving and fixing the volume to obtain 4L of sulfate solution with the total metal ion concentration of nickel, cobalt and manganese being 1 mol/L, adding 50g of ascorbic acid into the sulfate solution, slowly and parallelly dropwise adding the ascorbic acid, 0.4 mol/L ammonia water and 1 mol/L sodium hydroxide solution into a stirring reactor protected by nitrogen, controlling the pH to be 11.2 and the temperature to be 65 ℃, continuing to react for 16h after the addition is finished, and filtering to obtain a precursor Ni 1/3Co1/3Mn1/3(OH)2。
321g of dried precursor is added into an autoclave, hydrogen peroxide is added, the molar ratio of O/(Ni + Co + Mn) is 1.0, water is added according to the liquid-solid ratio L/S being 3:1, 151.2g of lithium hydroxide monohydrate is added to enable the molar ratio of L i/(Ni + Co + Mn) to be 1.03, the autoclave is sealed and heated to 220 ℃ and stirred, the heat preservation time is 5 hours, slurry is poured out after cooling, the slurry is directly dried for 4 hours at 100 ℃, the slurry is ground and uniformly mixed, and the ternary cathode material finished product is obtained after the slurry is roasted for 5 hours at 800 ℃ in a box-type muffle furnace.
Example 2
100g of nickel-cobalt-manganese system lithium ion battery anode waste is crushed, ground and subjected to alkaline leaching, filtered, dried and then placed in a muffle furnace to be roasted, the temperature is 500 ℃, the time is 2 hours, CO is slowly introduced during the process, and the mass of carbon in the CO is 4% of that of alkaline leaching residues. The roasted product is placed in water and stirred and CO is introduced 2When the mixture is immersed in water, the liquid-solid ratio is 5:1, and CO is introduced 2the molar weight of the solution is 4 times of the molar weight of lithium in the solid, the time is 1.0h, lithium-rich solution is obtained by filtering, filter residue is added into 1L hydrochloric acid solution with the concentration of 2.5 mol/L, the solution is stirred for 3 hours at the constant temperature of 40 ℃, chlorine salt solution containing cobalt, nickel and manganese is obtained by filtering, the recovery rate of each valuable element is 91.2 percent of lithium, 99.2 percent of cobalt, 98.5 percent of nickel and 99.0 percent of manganese, Na is added into the acid leaching solution 2S, removing Fe and Cu, adding NaF to remove Ca and Mg, and finally removing aluminum by hydrolysis to obtain impurity-removed liquid, wherein the components are shown in Table 2:
| Ni | Co | Mn | Cu | Fe | Al | Ca | Mg |
| 18.2g/L | 15.3g/L | 12.2g/L | <0.1ppm | <2.0ppm | <2.0ppm | <2.0ppm | <1.0ppm |
TABLE 2 post-purification nickel cobalt manganese sulfate solution composition
preparing solution according to the equimolar amount of nickel, cobalt and manganese, respectively adding 45.0g of cobalt chloride hexahydrate, 194.0g of nickel chloride hexahydrate and 89.6g of manganese chloride tetrahydrate into purified sulfate solution, dissolving and fixing the volume to obtain 1.5L of chloride solution with the total metal ion concentration of nickel, cobalt and manganese being 1.5 mol/L, adding 20g of ascorbic acid into the chloride solution, dropwise adding the ascorbic acid, 0.6 mol/L ammonia water and 1.5 mol/L sodium hydroxide solution into a nitrogen-protected stirring reactor in parallel, controlling the pH to be 11.0, controlling the temperature to be 55 ℃, continuing to react for 20 hours after the feeding is finished, and filtering to obtain a precursor Ni 0.5Co0.2Mn0.3(OH)2。
160g of dried precursor is added into an autoclave, water is added according to the liquid-solid ratio L/S of 2:1, 76g of lithium hydroxide monohydrate enables the molar ratio of L i/(Ni + Co + Mn) to be 1.04, the autoclave is sealed and heated to 200 ℃ and stirred, oxygen is introduced until the pressure is 3MPa, the temperature is kept for 6h, the slurry is poured out after cooling, the slurry is directly dried for 2h at 120 ℃, the slurry is ground and uniformly mixed, and the mixture is roasted for 4h at 850 ℃ in a box-type muffle furnace to obtain the ternary cathode material finished product.
The protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A method for preparing a ternary cathode material by recycling a waste lithium ion battery cathode material is characterized by comprising the following steps:
Step one, alkaline leaching aluminum removal: adding alkali liquor into the positive electrode waste to leach aluminum, filtering to obtain alkaline leaching residues and alkaline leaching solution, drying the alkaline leaching residues, and separately recovering aluminum from the alkaline leaching solution;
Step two, roasting/extracting lithium: mixing and roasting the alkaline leaching residue and a reducing agent, leaching with water and introducing carbon dioxide to extract lithium after roasting, filtering to obtain a lithium-rich solution and filter residue, and evaporating and crystallizing to obtain a lithium-containing product;
Step three, acid leaching: adding acid into the filter residue obtained in the second step for leaching, filtering to obtain a leaching solution and acid leaching residue, and recovering carbon from the acid leaching residue;
Step four, impurity removal: adding a vulcanizing agent into the pickle liquor to remove Fe and Cu, adding villiaumite to remove Ca and Mg, and finally removing aluminum by hydrolysis to obtain a solution after impurity removal;
step five, preparing a liquid mixture, namely detecting the concentration of nickel, cobalt and manganese in the liquid after impurity removal, adding soluble nickel salt, cobalt salt or manganese salt according to the proportion of nickel, cobalt and manganese components in a target product, and adding water to enable the concentration of total metal ions of nickel, cobalt and manganese to be 0.5-2.5 mol/L;
Step six, coprecipitation: slowly adding the solution obtained in the fifth step, a sodium hydroxide solution and dilute ammonia water into a stirring reactor under a protective atmosphere for coprecipitation, and filtering to obtain a precursor Ni xCoyMn1-x-y(OH)2；
step seven, hydro-thermal synthesis, namely adding a precursor, a lithium source, an additive and water into a high-pressure reaction kettle, wherein the additive is one or a mixture of hydrogen peroxide, oxygen and ozone, the dosage of lithium is L i/(Ni + Co + Mn) in a molar ratio of 1.0-1.07, the dosage of the additive is O/(Ni + Co + Mn) in a molar ratio of 0.1-10, and the liquid-solid ratio L/S is 1: 1-4: 1;
Step eight, drying/mixing: directly drying the hydrothermal product without solid-liquid separation, and drying the product by ball milling and mixing;
Step nine, roasting: roasting the mixed materials for 2-10 hours at the temperature of 750-900 ℃ to obtain a positive electrode material;
In the first step, the used anode waste is one or a mixture of more of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganate, lithium nickel cobalt aluminate and lithium-rich manganese-based solid solution;
In the second step, the reducing agent is solid reducing agent lignite, bituminous coal, anthracite or gaseous reducing agent CO and H 2The sum of the mass of C and H in the reducing agent is 4-20% of the mass of the anode waste, the roasting temperature is 400-700 ℃, and the roasting time is 0.5-4H; the liquid-solid ratio is 1: 1-10: 1 during water immersion, and CO is introduced 2The molar weight of the lithium-containing solid is 0.55-10 times of that of lithium in the solid, and the leaching time is 0.5-3 hours.
2. the method according to claim 1, wherein in the third step, the acid is one of sulfuric acid, nitric acid or hydrochloric acid, the liquid-solid ratio is 2: 1-20: 1, the concentration is 1-2.5 mol/L, and the acid leaching temperature is 20-90 ℃.
3. the method of claim 1, wherein the concentration of the sodium hydroxide used in the sixth step is 0.5-2.5 mol/L, the concentration of the dilute ammonia water is 0.2-1.0 mol/L, the shielding gas is one or a mixture of nitrogen and argon, the reaction temperature is 40-70 ℃, and the reaction time is 5-20 h.
4. the method according to claim 1, wherein in the seventh step, the precursor is fresh dry material or wet material, the hydrothermal temperature is 140-250 ℃, the heat preservation time is 1-6 h, the dosage of the additive is 0.4-4 of molar ratio O/(Ni + Co + Mn), and the liquid-solid ratio L/S is 1: 1-2: 1.
5. The method as claimed in claim 1, wherein the hydrothermal product is directly dried in the step eight, the drying temperature is 80-120 ℃, and the drying time is 2-10 h.
6. The method according to claim 1, wherein in the ninth step, the roasting temperature is 800-850 ℃ and the roasting time is 4-5 h.
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| CN110527835B (en) * | 2019-09-02 | 2020-07-07 | 清华大学 | Method for recycling soft package full components of waste ternary lithium battery |
| CN110729524A (en) * | 2019-11-12 | 2020-01-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for repairing lithium ion battery anode material |
| CN111430829B (en) * | 2020-03-11 | 2021-06-29 | 中南大学 | Method for recycling and regenerating waste lithium battery anode material under assistance of biomass waste |
| CN111733326A (en) * | 2020-07-03 | 2020-10-02 | 昆明理工大学 | Method for efficiently recycling ternary cathode material of waste lithium ion battery |
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