CN112830526B - Method for regenerating ternary precursor by using nickel-cobalt-manganese slag - Google Patents
Method for regenerating ternary precursor by using nickel-cobalt-manganese slag Download PDFInfo
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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 relates to the technical field of waste ternary cathode material recovery, and provides a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag. Mixing nickel-cobalt-manganese slag, water and a reducing agent, regulating the obtained mixed solution to be alkaline, and then mixing the mixed solution with ammonium salt to obtain mixed solution; and carrying out hydrothermal reaction on the mixed solution to obtain a ternary precursor. According to the invention, nickel cobalt manganese slag and a reducing agent are mixed for hydrothermal reaction, and under the action of the reducing agent, metal oxides in the nickel cobalt manganese slag are reduced into corresponding +2 valence metal hydroxides. The method provided by the invention directly reduces the nickel-cobalt-manganese slag into the ternary precursor, can realize the recycling of the waste ternary positive electrode material, and has great application prospects.
Description
Technical Field
The invention relates to the technical field of waste ternary cathode material recovery, in particular to a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag.
Background
The nickel cobalt lithium manganate ternary positive electrode material (NCM) has the advantages of high energy density, relatively low cost, excellent cycle performance and the like, and is one of the positive electrode materials with the most development prospect in the current mass production. In the future, as the sales volume of new energy automobiles continuously rises, the continuous expansion of the yield of the ternary battery drives the market of the ternary cathode material to further expand.
After the lithium ion battery is subjected to multiple charge and discharge cycles, the battery structure can be changed, so that the lithium ion battery is disabled and scrapped, and the production and the use of a large number of lithium ion batteries tend to bring about explosive generation of the waste lithium ion batteries. According to the scrapped quantity of the power lithium battery used by a commercial vehicle (3 years battery life) and a passenger vehicle (5 years battery life), with the rapid increase of the sales quantity of new energy automobiles, the retired peak of the power battery is also accompanied, and according to the report of a prospective industrial institute, the value of the metal element in the disassembled and recycled waste power battery is estimated, the recycling market scale of the Chinese power battery is over 50 hundred million yuan at present, 100 hundred million yuan is expected to be broken through in 2020, and the scale of 250 hundred million yuan can be reached in 2023.
At present, waste NCM is generally treated and recovered by a high-acid full-dissolution method, ni, co and Mn in the NCM exist in +2, +3 and +4 valences respectively, and a small amount of Ni (III) and Mn (III) exist. In order to convert high-valence Co (III), mn (III), ni (III) and Mn (IV) into low-valence Co (II), mn (II) and Ni (II) which are easier to be leached by acid, a proper amount of reducing agent is usually added, NCM is converted into leaching solution containing Ni, co, mn, li by adopting a high-acid total-dissolution method, the method involves the processes of high-acid dissolution, chemical precipitation or extraction and the like, and has the advantages of high acid-base consumption, high environmental protection pressure, long process flow, and additional waste generation, thus causing secondary pollution.
Patent CN110835117a discloses a method for selectively extracting lithium from waste ternary cathode materials, wherein lithium is extracted into water by means of roasting, water immersion and the like to obtain a lithium-rich solution, and the residual waste residue is nickel cobalt manganese slag, and the patent does not describe how the residual nickel cobalt manganese slag is further treated.
Disclosure of Invention
In view of this, the present invention provides a method for regenerating a ternary precursor using nickel cobalt manganese slag. The method provided by the invention can directly regenerate the ternary precursor by utilizing the nickel-cobalt-manganese slag remained after the selective lithium extraction of the ternary positive electrode material, and the regenerated ternary precursor can restore the morphology and electrochemical performance of the original ternary precursor.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag comprises the following steps:
mixing nickel cobalt manganese slag, water and a reducing agent, regulating the obtained mixed solution to be alkaline, and then mixing the mixed solution with ammonium salt to obtain a mixed solution; the nickel-cobalt-manganese slag is the residual slag after the lithium is selectively extracted from the waste nickel-cobalt lithium manganate ternary positive electrode material;
carrying out hydrothermal reaction on the mixed solution to obtain a ternary precursor; the hydrothermal reaction comprises a heating stage and a heat preservation stage which are sequentially carried out, wherein the temperature of the heat preservation stage is 250-380 ℃.
Preferably, the components in the mixed feed liquid further comprise a nickel source, a cobalt source and a manganese source.
Preferably, the reducing agent comprises one or more of sulfide, sulfite, thiosulfate, hydrazine, hydroxylamine and aldehyde.
Preferably, the sulfide comprises one or more of sodium sulfide, potassium sulfide, ammonium sulfide, zinc sulfide and hydrogen sulfide; the sulfite comprises one or more of sodium sulfite, ammonium sulfite, potassium sulfite, zinc sulfite and sodium bisulfite; the thiosulfate comprises one or more of sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate.
Preferably, the mass of the reducing agent is 8-40% of the mass of the nickel-cobalt-manganese slag.
Preferably, the reagent for adjusting the mixture to be alkaline comprises one or more of ammonia water, sodium hydroxide, sodium carbonate, potassium hydroxide and urea; and regulating the pH value of the mixed solution to 8.5-12.
Preferably, the ammonium salt comprises one or more of ammonium carbonate, ammonium bicarbonate and ammonium oxalate.
Preferably, the mass of the ammonium salt is 10-80% of the mass of the nickel-cobalt-manganese slag.
Preferably, the heat preservation period is 2-6 hours, and the pressure is 5-15 MPa.
Preferably, the heating stage comprises a first stage and a second stage which are sequentially carried out, wherein the first stage is used for heating from room temperature to 200 ℃, the heating rate is 1.5-3 ℃/min, and the second stage is used for heating from 200 ℃ to the temperature of the heat preservation stage, and the heating rate is 0.4-1.3 ℃/min.
The invention provides a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag, which comprises the following steps: mixing nickel cobalt manganese slag, water and a reducing agent, regulating the obtained mixed solution to be alkaline, and then mixing the mixed solution with ammonium salt to obtain a mixed solution; the nickel-cobalt-manganese slag is the residual slag after the lithium is selectively extracted from the waste nickel-cobalt lithium manganate ternary positive electrode material; carrying out hydrothermal reaction on the mixed solution to obtain a ternary precursor; the hydrothermal reaction comprises a heating stage and a heat preservation stage which are sequentially carried out, wherein the temperature of the heat preservation stage is 250-380 ℃. According to the invention, nickel cobalt manganese slag and a reducing agent are mixed for hydrothermal reaction, under the action of the reducing agent, metal oxide in the nickel cobalt manganese slag is reduced into corresponding +2 valence metal hydroxide, and the morphology and the particle size of a product are controlled by adding ammonium salt and controlling the hydrothermal reaction temperature, so that the morphology and the electrochemical performance of the original ternary precursor are finally recovered.
According to the method provided by the invention, the residual nickel cobalt manganese slag after the selective lithium extraction of the waste nickel cobalt lithium manganate ternary cathode material is used as a raw material to directly regenerate the ternary precursor, the whole process is free from purification, impurity removal, extraction and separation, the process flow is short, the cost is low, and the high acid is not required to be adopted to dissolve the nickel cobalt manganese slag, so that the problems of high acid and alkali consumption and high environmental protection pressure in the traditional high acid full-dissolution method are solved; the method provided by the invention can realize the recycling of the waste ternary cathode material, reduce the external dependence of cobalt, nickel and lithium resources in China, stabilize the cobalt resource price of which the downstream demand continuously increases at a high speed, and is beneficial to promoting the continuous healthy development of new energy automobiles in China, thereby having great application prospects.
In addition, when the ternary precursor is synthesized by the traditional method, metal salt is taken as a raw material, and metal ions and OH are adopted - Or CO 3 2- The method provided by the invention takes nickel cobalt manganese slag as a raw material, nickel, cobalt and manganese elements in the nickel cobalt manganese slag exist in the form of oxides, the oxides of nickel, cobalt and manganese undergo a reduction reaction under alkaline conditions, and the required OH is needed - The amount of the (B) is small, so that the cost for preparing the ternary precursor is lower, a large amount of ammonia water is saved, and the environmental protection pressure is relieved.
Furthermore, the medicaments adopted by the invention are common and low-cost industrial chemical raw materials, and the cost of regenerating the ternary precursor is lower.
The results of the examples show that: the morphology and the particle size of the ternary precursor regenerated by the method are similar to those of the original ternary precursor, and the ternary positive electrode material prepared by the regenerated ternary precursor has high discharge specific capacity and good charge-discharge cycle performance.
Drawings
FIG. 1 is a schematic flow chart of a regeneration ternary precursor according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of nickel cobalt manganese slag;
FIG. 3 is an SEM image of nickel cobalt manganese slag;
FIG. 4 is an XRD pattern of a lithium nickel cobalt manganese oxide ternary positive electrode material obtained by calcining lithium in example 1;
FIG. 5 is an SEM image of a ternary positive electrode material of lithium nickel cobalt manganese oxide obtained by calcining lithium in example 1;
FIG. 6 is an SEM image of a ternary precursor of example 1;
FIG. 7 is an SEM image of a ternary precursor of example 2;
FIG. 8 is an SEM image of a ternary precursor of example 3;
FIG. 9 is an SEM image of a ternary precursor of example 4;
FIG. 10 is an SEM image of the hydrothermal product of comparative example 1;
FIG. 11 is an SEM image of the hydrothermal product of comparative example 2;
fig. 12 is an SEM image of the hydrothermal product obtained in comparative example 3.
Detailed Description
The invention provides a method for regenerating a ternary precursor by utilizing nickel-cobalt-manganese slag, which comprises the following steps:
mixing nickel cobalt manganese slag, water and a reducing agent, regulating the obtained mixed solution to be alkaline, and then mixing the mixed solution with ammonium salt to obtain a mixed solution; the nickel-cobalt-manganese slag is the residual slag after the lithium is selectively extracted from the waste nickel-cobalt lithium manganate ternary positive electrode material;
carrying out hydrothermal reaction on the mixed solution to obtain a ternary precursor; the hydrothermal reaction comprises a heating stage and a heat preservation stage which are sequentially carried out, wherein the temperature of the heat preservation stage is 250-380 ℃.
In the invention, the nickel cobalt manganese slag is the residual slag after the selective lithium extraction of the waste nickel cobalt lithium manganate ternary positive electrode material; the main elements contained in the nickel-cobalt-manganese slag are nickel, cobalt, manganese and oxygen, wherein Ni, co and Mn exist in +2, +3 and +4 valences respectively. The invention has no special requirements on the type of the nickel cobalt lithium manganate ternary positive electrode material, and the common waste nickel cobalt lithium manganate ternary positive electrode materials in the field can be specifically like NCM523 and NCM622. In a specific embodiment of the present invention, the selective lithium extraction is preferably performed according to the method disclosed in CN110835117a, comprising the following specific steps:
mixing waste ternary cathode material powder with acid, and performing primary roasting to obtain a primary roasting product;
mixing the first-stage roasting product with an auxiliary agent, and carrying out second-stage roasting to obtain a second-stage roasting product;
and (3) putting the second-stage roasting product into water for leaching, and carrying out solid-liquid separation to obtain a lithium-rich solution.
The solid material obtained after solid-liquid separation is rich in a large amount of cobalt, nickel and manganese metal elements, namely the nickel-cobalt-manganese slag.
The invention mixes nickel cobalt manganese slag, water and reducing agent, adjusts the obtained mixed liquid to be alkaline, and then mixes the mixed liquid with ammonium salt to obtain mixed liquid. In the present invention, the water is preferably deionized water; the reducing agent preferably comprises one or more of sulfide, sulfite, thiosulfate, hydrazine, hydroxylamine and aldehyde; the sulfide preferably comprises one or more of sodium sulfide, potassium sulfide, ammonium sulfide, zinc sulfide and hydrogen sulfide; the sulfite comprises one or more of sodium sulfite, ammonium sulfite, potassium sulfite, zinc sulfite and sodium bisulfite; the thiosulfate comprises one or more of sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate; the present invention is not particularly limited to the kind of the aldehyde, and any aldehyde having a reducing property, such as formaldehyde, which is well known to those skilled in the art, may be used. In the present invention, the mass of the reducing agent is preferably 8 to 40% of the mass of the nickel cobalt manganese slag, more preferably 10 to 35%.
The invention adjusts the mixed solution of nickel cobalt manganese slag, water and reducing agent to be alkaline, preferably to be adjusted to be pH value of 8.5-12, more preferably to be adjusted to be pH value of 9-11; in the present invention, the reagent used for adjusting the mixture to be alkaline is preferably one or more of ammonia water, sodium hydroxide, sodium carbonate, potassium hydroxide and urea; the invention adjusts the mixed solution to alkalinity, and can ensure OH in the mixed system - Has a certain concentration, and is favorable for complete precipitation of the supplementary elements.
In the present invention, the ammonium salt preferably includes one or more of ammonium carbonate, ammonium bicarbonate and ammonium oxalate; the mass of the ammonium salt is preferably 10-80% of the mass of the nickel-cobalt-manganese slag, more preferably 15-40%; the ammonium salt provides ammonium ions, so that the morphology of the product can be controlled, and the sphericity of the product can be improved.
In the invention, the components in the mixed feed liquid also comprise a nickel source, a cobalt source and a manganese source; the nickel source is preferably nickel sulfate, the cobalt source is preferably cobalt sulfate, the manganese source is preferably manganese sulfate, trace nickel, cobalt and manganese lost in the selective lithium extraction process of the waste nickel cobalt lithium manganate ternary positive electrode material are supplemented by adding the nickel source, the cobalt source and the manganese source, and the supplementing amount of the nickel source, the cobalt source and the manganese source is preferably controlled according to the model of the waste nickel cobalt lithium manganate ternary positive electrode material, for example, when the waste nickel cobalt lithium manganate ternary positive electrode material is NCM523 (namely, the molar ratio of nickel element, cobalt element and manganese element is 5:2:3), the molar ratio of nickel element, cobalt element and manganese element in a mixture of nickel source, cobalt source and manganese source is 5:2:3 by supplementing the nickel source, cobalt source and manganese source; in the specific embodiment of the invention, the content of nickel, cobalt and manganese in the nickel-cobalt-manganese slag is preferably detected, and then the complementary amounts of the nickel source, the cobalt source and the manganese source are determined by combining the detection result and the model of the ternary positive electrode material, and if the content of nickel, cobalt and manganese in the nickel-cobalt-manganese slag accords with the required molar ratio, the nickel source, the cobalt source and the manganese source can be not added additionally.
After the mixed feed liquid is obtained, the mixed feed liquid is subjected to hydrothermal reaction to obtain the ternary precursor. In the invention, the hydrothermal reaction comprises a heating stage and a heat preservation stage which are sequentially carried out, wherein the heating stage comprises a first stage and a second stage which are sequentially carried out, the first stage is heated from room temperature to 200 ℃, the heating rate is 1.5-3 ℃/min, preferably 2-2.5 ℃/min, and the second stage is heated from 200 ℃ to the temperature of the heat preservation stage, and the heating rate is 0.4-1.3 ℃/min, preferably 0.5-1 ℃/min; the temperature of the heat preservation stage is 250-380 ℃, preferably 280-350 ℃, the time is preferably 2-6 h, more preferably 3-4 h, the pressure is preferably 5-15 MPa, more preferably 8-12 MPa; the hydrothermal reaction is preferably carried out in an autoclave; the invention carries out hydrothermal reaction under higher pressure, the temperature rising process in a low temperature area (room temperature to 200 ℃) has little influence on the reaction, so that the temperature can be raised by adopting higher temperature rising rate, and the influence on the reaction is aggravated along with the severe change of gas pressure when the temperature rises in a high temperature area (more than 200 ℃), thus the lower temperature rising rate needs to be controlled; the temperature rising rate is controlled within the range of the invention, so that the stable proceeding of the hydrothermal reaction can be ensured.
The invention controls the temperature of the hydrothermal reaction heat preservation stage to be 250-380 ℃, can improve the reduction reaction rate, and is beneficial to the control of the morphology of the precursor.
In the hydrothermal reaction process, the nickel-cobalt-manganese oxide is subjected to reduction reaction under the action of a reducing agent to generate corresponding +2 valence metal hydroxide, and the crushed high valence nickel-cobalt-manganese oxide is directly reduced and restored to the morphology of the ternary precursor. Taking the reducing agent as sodium sulfide or ammonium sulfide as an example to illustrate the reaction occurring in the hydrothermal reaction process, the reaction formula can be expressed approximately as follows:
when the reducing agent is sodium sulfide:
4MnO 2 +Na 2 S+4H 2 O＝4Mn(OH) 2 +Na 2 SO 4
4Co 3 O 4 +Na 2 S+12H 2 O＝12Co(OH) 2 +Na 2 SO 4
when the reducing agent is ammonium sulfide:
4MnO 2 +(NH 4 ) 2 S+4H 2 O＝4Mn(OH) 2 +(NH 4 ) 2 SO 4
4Co 3 O 4 +(NH 4 ) 2 S+12H 2 O＝12Co(OH) 2 +(NH 4 ) 2 SO 4
NiO can be converted into Ni (OH) with the added auxiliary agent under the high-temperature condition 2 。
After the hydrothermal reaction is finished, the method preferably comprises the steps of cooling and filtering product feed liquid, and then washing and drying filter cakes in sequence to obtain a ternary precursor; the washing times are preferably 2-5 times, and the washing detergent is preferably deionized water; the invention has no special requirement on the drying temperature, and can completely dry and remove the water in the filter cake. In the invention, the ternary precursor is specifically nickel cobalt manganese hydroxide, and the chemical formula is Ni x Co y Mn (1-x-y) (OH) 2 The morphology of the obtained nickel cobalt lithium manganate ternary positive electrode material is spherical, and the particle size is 4-10 nm.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Fig. 1 is a schematic flow chart of a ternary precursor regeneration in an embodiment of the present invention, wherein nickel cobalt manganese slag is a solid material remaining after selective lithium extraction of ternary waste, the nickel cobalt manganese slag and a reducing agent are mixed and subjected to component replenishment, and then hydrothermal regeneration is performed to obtain a ternary precursor material, and the ternary precursor material is subjected to high-temperature solid phase regeneration to obtain a ternary cathode material.
The nickel-cobalt-manganese slag in the examples is obtained by the following steps:
collecting waste nickel cobalt lithium manganate ternary positive electrode waste (NCM 523 type or NCM622 type), grinding and crushing the waste nickel cobalt lithium manganate ternary positive electrode waste into powder, mixing the powder with oxalic acid in a mass ratio of 1:0.6, uniformly stirring, placing the mixture into a muffle furnace, roasting for one period of time at 180 ℃ for 60min, closing the muffle furnace, mixing the roasted product with potassium oxalate in a mass ratio of 1:0.2 when the roasted product is cooled to room temperature, placing the mixed product into the muffle furnace for two-stage roasting at a roasting temperature of 600 ℃ for 100min; and after the second-stage roasting is finished, mixing the second-stage roasting product with water in a mass ratio of 1:5, leaching for 40min at room temperature, carrying out solid-liquid separation after leaching is finished to obtain a lithium-rich solution, and drying the rest solid phase material to obtain nickel-cobalt-manganese slag.
Fig. 2 is an XRD pattern of the obtained nickel cobalt manganese slag, and it can be seen from fig. 2 that the existence state of nickel cobalt manganese in the nickel cobalt manganese slag is mainly oxide.
Fig. 3 is an SEM image of the obtained nickel-cobalt-manganese slag, and it can be seen from fig. 3 that the morphology of the nickel-cobalt-manganese slag is irregular granular.
Example 1
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 523 type) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of the nickel to the cobalt to the manganese is 5:2:3. Weighing 800mL of deionized water, accurately weighing 2.5g of sodium sulfide, uniformly stirring all the raw materials, pouring the raw materials into a high-pressure reaction kettle, adjusting the pH value of the mixed feed liquid to 8.5 by using ammonia water, adding 8.0g of ammonium carbonate, screwing the high-pressure reaction kettle according to specifications, setting the reaction temperature to 280 ℃, controlling the heating rate to 1.5 ℃/min before 200 ℃, controlling the heating rate to 0.4 ℃/min after 200 ℃, heating to 280 ℃, keeping the temperature constant for reaction for 5h, controlling the pressure in the high-pressure reaction kettle to 6.5MPa, stopping heating after the reaction is finished, filtering, washing a filter cake for 2 times, and drying to obtain the ternary precursor.
And (3) calcining the ternary precursor with lithium to obtain the nickel cobalt lithium manganate ternary positive electrode material, wherein the addition amount of lithium is 1.08 times of the chemical dosage ratio, and the calcining temperature is 850 ℃. The electrochemical performance of the obtained ternary positive electrode material is tested, and the result shows that: the initial discharge specific capacity of 0.1C can reach 152.3mAh/g, the discharge cycle is 100 times under 0.1C, the discharge capacity reaches 95.7% of the initial capacity, and the battery has good charge-discharge cycle performance.
Fig. 4 is an XRD pattern of a lithium nickel cobalt manganese oxide ternary positive electrode material obtained by calcination of lithium. As can be seen from fig. 5, the XRD peaks of the resulting lithium nickel cobalt manganate ternary cathode material are consistent with standard cards.
Fig. 5 is an SEM image of a lithium nickel cobalt manganese oxide ternary positive electrode material obtained by calcination of lithium. As can be seen from fig. 5, the morphology of the obtained nickel cobalt lithium manganate ternary cathode material is spherical.
Example 2
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 523 type) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of the nickel to the cobalt to the manganese is 5:2:3. Weighing 1000mL of deionized water, accurately weighing 4.5g of ammonium sulfide, uniformly stirring all the raw materials, pouring the raw materials into a high-pressure reaction kettle, adding sodium hydroxide to adjust the pH of the mixed feed liquid to 9.0, adding 10.8g of ammonium bicarbonate, tightening the high-pressure reaction kettle according to specifications, setting the reaction temperature to 300 ℃, controlling the heating rate to 3 ℃/min before 200 ℃, controlling the heating rate to 1 ℃/min after 200 ℃, heating to 300 ℃, reacting for 4 hours at constant temperature, controlling the pressure in the high-pressure reaction kettle to 7.8MPa, stopping heating after the reaction is finished, filtering and washing a filter cake for 4 times, and drying to obtain the ternary precursor.
And (3) calcining the ternary precursor with lithium (the conditions are the same as those of the embodiment 1) to obtain the nickel cobalt lithium manganate ternary positive electrode material. The electrochemical performance of the obtained ternary positive electrode material is tested, and the result shows that: the initial discharge specific capacity of 0.1C can reach 153.1mAh/g, the discharge cycle is 100 times under 0.1C, the discharge capacity reaches 96.1% of the initial capacity, and the battery has good charge-discharge cycle performance.
Example 3
Weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 622) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of nickel to cobalt to manganese is 6:2:2. measuring 700mL of deionized water, accurately weighing 1.5g of ammonium sulfide and 1.5g of ammonium sulfite, uniformly stirring all the raw materials, pouring the raw materials into a high-pressure reaction kettle, adding sodium hydroxide to adjust the pH value of the mixed material liquid to 9.5, adding 10.5g of ammonium oxalate, screwing the high-pressure reaction kettle according to specifications, setting the reaction temperature to 350 ℃, controlling the heating rate to 2 ℃/min before 200 ℃, controlling the heating rate to 1 ℃/min after 200 ℃, heating to 350 ℃, carrying out constant-temperature reaction for 3h after the temperature is increased, stopping heating after the reaction is finished, filtering, washing a filter cake for 3 times, and drying to obtain the ternary precursor.
And (3) calcining the ternary precursor with lithium (the conditions are the same as those of the embodiment 1) to obtain the nickel cobalt lithium manganate ternary positive electrode material. The electrochemical performance of the obtained ternary positive electrode material is tested, and the result shows that: the initial discharge specific capacity of 0.1C can reach 155.3mAh/g, the discharge cycle is 100 times under 0.1C, the discharge capacity reaches 95.6% of the initial capacity, and the battery has good charge-discharge cycle performance.
Example 4
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 622) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of nickel to cobalt to manganese is 6:2:2. Weighing 1050mL of deionized water, accurately weighing 2.0g of sodium sulfide and 1.2g of ammonium sulfite, uniformly stirring all the raw materials, pouring into a high-pressure reaction kettle, adding sodium hydroxide to adjust the pH value of the mixed material liquid to 9.5, adding 12.8g of ammonium oxalate, tightening the high-pressure reaction kettle according to specifications, setting the reaction temperature to 360 ℃, controlling the heating rate to 2.5 ℃/min before 200 ℃, controlling the heating rate to 1 ℃/min after 200 ℃, heating to 360 ℃, carrying out constant-temperature reaction for 2.5h after 360 ℃, stopping heating after the reaction, filtering, washing a filter cake for 3 times, and drying to obtain a ternary precursor.
And (3) calcining the ternary precursor with lithium (the conditions are the same as those of the embodiment 1) to obtain the nickel cobalt lithium manganate ternary positive electrode material. The electrochemical performance of the obtained ternary positive electrode material is tested, and the result shows that: the initial discharge specific capacity of 0.1C can reach 155.6mAh/g, the discharge cycle is 100 times under 0.1C, the discharge capacity reaches 96.3% of the initial capacity, and the battery has good charge-discharge cycle performance.
Comparative example 1
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 523 type) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of the nickel to the cobalt to the manganese is 5:2:3. Weighing 800mL of deionized water, stirring uniformly, pouring into a high-pressure reaction kettle, adding ammonia water to adjust the pH value of the mixed feed liquid to 8.5, adding 8.0g of ammonium carbonate, tightening the high-pressure reaction kettle according to specifications, setting the reaction temperature to 280 ℃, controlling the heating rate to 2 ℃/min before 200 ℃, controlling the heating rate to 1 ℃/min after 200 ℃, reacting at a constant temperature after 280 ℃ for 5 hours, controlling the pressure in the high-pressure reaction kettle to 6.2MPa, stopping heating, filtering and washing a filter cake for 2 times, filtering out substances which are still black, and drying to obtain a product.
The hydrothermal reaction product was calcined with lithium as in example 1 and the electrochemical properties of the resulting ternary cathode material were tested, showing that: the specific capacity of the first discharge of 0.1C is only 65.7mAh/g, and the charge-discharge cycle performance is poor, the attenuation is fast, and the electrochemical performance cannot be recovered.
Comparative example 2
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (523 type) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of nickel to cobalt to manganese is 5:2:3. 1000mL of deionized water is measured, 3.5g of ammonium sulfide is accurately weighed, the mixture is added into nickel cobalt manganese slag, the mixture is stirred uniformly, the mixture is poured into a 2L beaker, sodium hydroxide is added to adjust the pH value of the mixture to 9.0, 10.8g of ammonium bicarbonate is added, the mixture is continuously stirred in a hydrothermal pot, the water bath set temperature is 60 ℃, the mixture is reacted for 4 hours at the constant temperature after the water bath reaches 60 ℃, heating is stopped, the filter cake is filtered and washed for 2 times, and the product is obtained after the filter cake is dried.
The above product was lithium calcined as in example 1 and the electrochemical properties of the resulting ternary cathode material were tested, showing: the specific capacity of the first discharge of 0.1C is only 72.3mAh/g, and the charge-discharge cycle performance is poor, the attenuation is fast, and the electrochemical performance cannot be recovered.
Comparative example 3
And weighing 20g of nickel-cobalt-manganese slag remained after the ternary waste (NCM 622) is selectively extracted with lithium, and supplementing nickel sulfate, cobalt sulfate and manganese sulfate to ensure that the molar ratio of nickel to cobalt to manganese is 6:2:2. 700mL of deionized water is measured, 1.5g of ammonium sulfide and 2.5g of ammonium sulfite are accurately weighed and stirred uniformly, the mixture is poured into a high-pressure reaction kettle, sodium hydroxide is added to adjust the pH value of the mixed solution to 9.5, ammonium oxalate is added to 15.5g, the high-pressure reaction kettle is screwed up according to the specification, the reaction temperature is set to 150 ℃, the constant temperature reaction is carried out for 3 hours after the temperature is raised to 150 ℃, the pressure in the high-pressure reaction kettle is 0.1MPa, the heating is stopped, the mixture is filtered, stirred and washed for 2 times, and the product is obtained after drying.
The hydrothermal product was lithium calcined as in example 1 and the electrochemical properties of the resulting ternary cathode material were tested, showing: the specific capacity of the first discharge of 0.1C is only 105.7mAh/g, the charge-discharge cycle performance is poor, the decay is fast, and the electrochemical performance cannot be recovered.
Fig. 6 to 9 are SEM images of ternary precursors obtained in examples 1 to 4 in this order, and fig. 10 to 12 are SEM images of products obtained in comparative examples 1 to 3 in this order. As can be seen from fig. 6 to 9, the morphology of the ternary precursor obtained in examples 1 to 4 is uniform spherical particles, and as can be seen from fig. 3, the morphology of the ternary precursor obtained after regeneration is greatly changed compared with the morphology of the raw material (nickel cobalt manganese slag), and the spherical morphology is basically recovered. As can be seen from FIGS. 10 to 12, the hydrothermal products obtained in comparative examples 1 to 3 are mostly irregular particles, and the morphology of the product is not completely recovered to the spherical morphology, but some scattered particles exist, so that the electrochemical performance is poor, although the morphology of the product is changed compared with that of the nickel cobalt manganese slag in FIG. 3.
According to the results of comparative examples 1 to 3, it can be seen that the reducing agent and the hydrothermal reaction temperature have a great influence on the morphology of the product, and only the hydrothermal reaction temperature is controlled within the scope of the present invention, the morphology of the obtained product is not recovered under the condition that the reducing agent is not added (comparative example 1), the electrochemical performance of the product is poor, and the reducing agent is added, but the reduction reaction cannot be effectively performed under the condition that the hydrothermal reaction temperature does not meet the requirements of the present invention (comparative examples 2 to 3), the recovery affecting the morphology of the ternary precursor is performed, and the electrochemical performance of the cathode material prepared by using the hydrothermal product is poor.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The method for regenerating the ternary precursor by using the nickel-cobalt-manganese slag is characterized by comprising the following steps of:
mixing nickel-cobalt-manganese slag, water and a reducing agent, regulating the pH value of the obtained mixed solution to 8.5-12, and then mixing with ammonium salt to obtain mixed solution; the nickel-cobalt-manganese slag is the residual slag after the lithium is selectively extracted from the waste nickel-cobalt lithium manganate ternary positive electrode material; the reducing agent is sulfide;
carrying out hydrothermal reaction on the mixed solution to obtain a ternary precursor; the hydrothermal reaction comprises a heating stage and a heat preservation stage which are sequentially carried out, wherein the temperature of the heat preservation stage is 280-380 ℃, the time is 2-6 h, and the pressure is 5-15 MPa;
the temperature rising stage comprises a first stage and a second stage which are sequentially carried out, wherein the temperature rising rate of the first stage is 1.5-3 ℃/min from room temperature to 200 ℃, and the temperature rising rate of the second stage is 0.4-1.3 ℃/min from 200 ℃ to the temperature of the heat preservation stage.
2. The method of claim 1, wherein the components in the mixed liquor further comprise a nickel source, a cobalt source, and a manganese source.
3. The method of claim 1, wherein the sulfide comprises one or more of sodium sulfide, potassium sulfide, ammonium sulfide, zinc sulfide, and hydrogen sulfide.
4. A method according to claim 1 or 3, wherein the mass of the reducing agent is 8-40% of the mass of the nickel cobalt manganese slag.
5. The method according to claim 1, wherein the reagent for adjusting the mixture to alkaline comprises one or more of ammonia water, sodium hydroxide, sodium carbonate, potassium hydroxide and urea.
6. The method of claim 1, wherein the ammonium salt comprises one or more of ammonium carbonate, ammonium bicarbonate, and ammonium oxalate.
7. The method according to claim 1 or 6, wherein the mass of the ammonium salt is 10-80% of the mass of the nickel cobalt manganese slag.
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