CN109921008B - Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule - Google Patents
Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule Download PDFInfo
- Publication number
- CN109921008B CN109921008B CN201910040438.5A CN201910040438A CN109921008B CN 109921008 B CN109921008 B CN 109921008B CN 201910040438 A CN201910040438 A CN 201910040438A CN 109921008 B CN109921008 B CN 109921008B
- Authority
- CN
- China
- Prior art keywords
- manganese
- cobalt
- nickel
- solution
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A method for preparing a nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules comprises the following steps: after the manganese nodules are dried and crushed, the manganese nodules are uniformly mixed with a reducing agent and a slag former, and reduction smelting is carried out to obtain the cobalt-nickel-copper-iron molten alloy and furnace slag. And (3) spraying the molten alloy to prepare powder, performing enhanced leaching, and performing solid-liquid separation to obtain a mixed solution of the iron rust slag and the cobalt, nickel, copper and manganese. And deeply purifying the cobalt-nickel-copper-manganese mixed leaching solution, and removing impurities to obtain a deeply purified cobalt-nickel-manganese mixed sulfuric acid solution. And finally, blending the molar ratio of cobalt, nickel and manganese in the cobalt, nickel and manganese mixed sulfuric acid solution according to the target requirement, putting the mixture into a reaction kettle in parallel with sodium hydroxide and ammonia water, carrying out synthetic reaction under the nitrogen protection atmosphere, aging, filtering, washing and drying to obtain the catalyst. The invention directly prepares the nickel-cobalt-manganese ternary cathode material precursor from a manganese nodule source, and realizes the aims of maximum utilization rate of mineral resources, minimum energy consumption and minimum environmental burden.
Description
Technical Field
The invention belongs to the technical field of preparation of nickel-cobalt-manganese ternary cathode materials, and particularly relates to a method for preparing a precursor of a nickel-cobalt-manganese ternary cathode material by using manganese nodules.
Background
The nickel-cobalt-manganese ternary positive electrode material has the advantages of high specific capacity, stable cycle performance, good safety performance and the like, has a very wide application prospect in a lithium ion power battery, is a product very close to lithium cobaltate, has a cost performance far higher than that of the lithium cobaltate, has a capacity 10-20% higher than that of the lithium cobaltate, is one of novel battery materials which can possibly replace the lithium cobaltate, is called as a third-generation lithium ion battery positive electrode material, and gradually occupies a leading position at a year growth rate of 20% in the domestic demand of the positive electrode material. The Ministry of industry and belief in China brought the nickel-cobalt-manganese ternary material into a high and new technology product of key development of 'twelve five new materials industry' planning in 2012. At present, the process technology for preparing the nickel-cobalt-manganese ternary material by using high-purity cobalt, nickel, manganese and lithium salt as raw materials and adopting a coprecipitation method is basically mature in China, and large-scale production is realized in enterprises of Hunan China fir, Xiamen tungsten industry, Beijing Dangshi technology and the like.
The manganese nodule is a rich submarine mineral resource, has large reserve and wide distribution, has important strategic significance, and is rich in considerable nickel, cobalt and manganese elements. In the early development stage of manganese nodule, the utilization value is mainly to extract valuable metals. With the rapid expansion of global economic activities, the resource consumption speed is obviously accelerated, the metal resources available for exploitation on land are gradually exhausted, the manganese nodule mineral resources become important sources for acquiring various metal resources by human beings, and the 21 st century becomes the marine century of human beings.
At present, researchers provide a variety of smelting processes aiming at extraction and utilization of manganese nodule, but generally, various valuable metals are separated and obtained by a traditional metallurgy method, the process flow is long, the recovery rate is low, and the additional value of the prepared product is low, so that the development of a short-flow process technical route with high product additional value is very necessary. Generally speaking, the traditional resource utilization mode is to separate various components in mineral resources by traditional metallurgy technology to obtain pure chemical and metallurgical raw materials, and then to recombine various components by material preparation technology to obtain high-value materials. Changes the extensive resource utilization mode which has low added value and is at the cost of environmental sacrifice at present, and realizes the clean high-value utilization of the nonferrous metal resources. Namely, the metal or inorganic non-metal material is directly prepared from a source processing link, so that the aims of maximum utilization rate of mineral resources, minimum energy consumption and minimum environmental burden are achieved.
At present, a method for preparing a precursor of a nickel-cobalt-manganese ternary cathode material by taking manganese nodule as a raw material is not reported.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules, aiming at the defects of the prior art, wherein the prepared positive electrode material precursor is used for preparing a positive electrode material, and has large discharge capacity and good discharge stability.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing a nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules comprises the following steps:
(1) crushing and drying the manganese nodules; mixing the crushed and dried manganese nodules, coke, quartz and quicklime to obtain a mixed material; in the mixed material, coke accounts for 5-20% of the total mass of the mixed material, quartz accounts for 3-10% of the total mass of the mixed material, crushed and dried manganese nodules account for 60-85% of the total mass of the mixed material, quicklime accounts for 5-10% of the total mass of the mixed material, and CaO in the quicklime/SiO in the quartz2Mass ratio of<1.5；
(2) Reducing and smelting the mixed material obtained in the step (1) at the temperature of 1300-1600 ℃ to obtain molten nickel, cobalt, manganese, iron and copper (a small amount of) alloy, and discarding slag;
(3) adding the molten nickel, cobalt, manganese, iron and copper alloy obtained in the step (2) into an atomization powder making device, and making powder by high-pressure nitrogen gas spraying, wherein the particle size of the powder is controlled to be less than or equal to 100 meshes, so as to obtain alloy powder;
(4) selective leaching of alloy powder: adding catalyst ammonium sulfate into sulfuric acid solution (the concentration of the sulfuric acid solution is 2-4 mol/L), heating to 70-90 ℃, preserving heat, continuously introducing ozone, adding the alloy powder obtained in the step (3) (the mass ratio of the alloy powder to the sulfuric acid solution is 1: 6-12), and stirring for 2-6 hours;
(5) under the condition of keeping stirring in the step (4), introducing hydrogen peroxide into the step (4), cooperating with ozone for oxidation leaching, controlling the pH value at the end point of the reaction to be 3-5, and carrying out solid-liquid separation after the reaction is carried out for 2-6h to obtain iron slag and leachate containing nickel, cobalt, manganese and copper;
(6) adding MnS into the leachate containing nickel, cobalt, manganese and copper obtained in the step (5) to deeply remove Cu, and performing solid-liquid separation to obtain an acidic leachate containing Ni, Co and Mn;
the mol ratio of MnS to Cu in the leaching solution containing nickel, cobalt, manganese and copper is 1-1.6: 1;
(7) adding NaF into the acidic leaching solution containing Ni, Co and Mn obtained in the step (6), deeply removing Ca and Mg, and carrying out solid-liquid separation to obtain a high-purity acidic solution containing Ni, Co and Mn;
the ratio of NaF to the sum of the amounts of Ca and Mg in the acid leaching solution containing Ni, Co and Mn is 2-3: 1.
(8) Adjusting the pH value of the high-purity acidic solution containing Ni, Co and Mn obtained in the step (7) to 5-6 by adopting NaOH solution, and removing Ni from the solution2+、Co2+、Mn2+Precipitating all other cations with sodium hydroxide, and filtering to obtain a mixed solution A;
(9) adjusting the molar ratio of nickel, cobalt and manganese in the mixed solution A obtained in the step (8) to (0.4-0.9) by using nickel sulfate, cobalt sulfate and manganese sulfate: (0.05-0.4): (0.05-0.4), and adjusting the pH to 5-6 by adopting a sodium hydroxide solution or a sulfuric acid solution to obtain a mixed solution B;
(10) adding ammonia water A, a sodium hydroxide solution and the mixed solution B obtained in the step (9) into a reactor filled with a base solution at the same time to obtain a mixture C, continuously stirring for 10-18h at the temperature of 30-60 ℃ under the protection of a nitrogen atmosphere for precipitation reaction, and obtaining a nickel-cobalt-manganese mixed precipitate after the precipitation is finished; the concentration of the ammonia water A is 0.4-0.8 mol/L;
(11) adding a sodium hydroxide solution (the mass concentration of the sodium hydroxide is 10-20%, and the liquid-solid mass ratio of the sodium hydroxide solution to the nickel-cobalt-manganese mixed precipitate is 10-15: 1) into the nickel-cobalt-manganese mixed precipitate obtained in the step (10), uniformly stirring, aging at the temperature of 30-70 ℃ for 0.5-2h, and sequentially washing, filtering and vacuum drying after the aging is finished to finally obtain the nickel-cobalt-manganese ternary cathode material precursor.
Further, in the step (1), the manganese nodule contains nickel, cobalt, manganese and other elements.
Further, in the step (1), crushing means crushing the manganese nodules until the particle size is less than or equal to 60 meshes.
Further, in the step (1), drying means drying the crushed manganese nodules until the mass content of water is less than or equal to 15%.
Further, in the step (2), the reduction smelting time is 30-120 min.
Further, in the step (3), the pressure of the high-pressure nitrogen is 0.8-2.5 MPa.
Further, in the step (4), the dosage of the ammonium sulfate is 10-80 g/(L sulfuric acid solution). In the step, the precipitate obtained by selective leaching of the alloy powder contains almost all elements such as Fe, tungsten and the like in the raw material, and Fe and tungsten in the leaching solution are trace.
Further, in the step (4), the flow of the introduced ozone is 0.5-3L/min.
Further, in the step (5), the volume of the hydrogen peroxide is 10-50% of the volume of the raw sulfuric acid solution in the step (4). (the concentration of hydrogen peroxide is preferably 30 to 80 g/l)
Further, in the step (4) and the step (5), the stirring speed is 500-1500 r/min.
Further, in the step (6), Cu is contained in the acidic leaching solution containing Ni, Co and Mn2+The concentration is less than or equal to 0.004 g/L.
Further, in the step (7), Ca is contained in the high-purity acid solution containing Ni, Co and Mn2+Concentration is less than or equal to 0.004g/L, Mg2+The concentration is less than or equal to 0.004 g/L.
Further, in the step (9), the total molar concentration of the nickel, cobalt and manganese elements in the mixed solution B is 0.8-2.0 mol/L.
Further, in the step (10), the molar ratio of the ammonium ion, the sodium hydroxide and the nickel-cobalt-manganese element in the mixture C is (0.4-0.8): (1.8-2.2): 1.
further, in the step (10), the base solution is prepared by dissolving ammonia B and sodium hydroxide in deionized water, the pH of the base solution is 10-12, and the molar ratio of ammonium ions to sodium hydroxide in the base solution is (0.5-1.5): 1. the volume of the base solution is 5-10% of the volume of the mixed solution B.
Further, in the step (11), the vacuum drying temperature is 80-110 ℃, the time is 2-5h, and the water content after drying is less than or equal to 1.0 wt%.
The invention adopts the pyrometallurgical reduction smelting, can realize the enrichment of metals such as nickel, cobalt and manganese, can obtain the molten alloy of the metals such as nickel, cobalt, manganese, copper and iron; the molten alloy is further sprayed to prepare powder, and the obtained alloy powder has the particle size of-100 meshes (less than 74 mu m), so that the problem that the alloy is tough and difficult to break can be solved; the alloy powder is selectively leached by adopting the ozone and hydrogen peroxide in a synergistic oxidation manner, so that the leaching effect of nickel, cobalt, manganese and copper in the alloy powder is good, the leaching rate reaches 99%, iron and tungsten almost completely precipitate into slag, and the iron, tungsten and target elements can be thoroughly separated. And (2) deeply purifying impurity elements such as Cu, Ca, Mg and the like in the leachate by adopting MnS, NaF and NaOH, adjusting the concentration of nickel, cobalt, manganese, ammonium and the like in the purified solution, and adding sulfuric acid and NaOH to adjust the pH value to obtain the high-purity nickel-cobalt-manganese-ammonium mixed solution.
And adding the prepared precipitation solution and the mixed solution into a reaction kettle filled with a base solution for precipitation reaction, adopting nitrogen protection in the reaction kettle, obtaining a nickel-cobalt-manganese mixed precursor after the reaction is finished, and aging, washing, filtering and drying the mixed precursor to obtain the nickel-cobalt-manganese ternary cathode material precursor.
The key reaction formula of the invention is as follows:
the reaction of reduction smelting in the above (2) is:
MeO+C→Me+CO↑（Me=Ni、Co、Mn、Cu、Fe） （1）
the reaction of the synergistic oxidation leaching in the step (5) is as follows:
2O3+H2O2→2·OH+3O2（2）
Me+·OH+2H+→Me2++H2O（Me=Ni、Co、Mn、Cu） （3）
Fe+·OH +H2O→FeOOH↓+H+（4）
2Fe+3·OH→Fe2O3+3H+（5）
the deep purification reaction in (6) and (7) above is:
MnS+CuSO4→CuS↓+MnSO4（6）
2NaF+Ca2+→CaF2↓+2Na+（7）
2NaF+Mg2+→MgF2↓+2Na+（8）
the reaction of nickel-cobalt-manganese coprecipitation in the step (10) is as follows:
xNi2++yCo2++（1-x-y）Mn2++2OH-→ NixCoyMn（1-x-y）(OH)2↓ （9）
the nickel, cobalt and manganese elements in the manganese nodule are completely matched with the metal elements required for preparing the nickel-cobalt-manganese ternary material, so that the manganese nodule is used as a raw material to prepare the precursor of the nickel-cobalt-manganese ternary positive electrode material with high added value, the resource bottleneck of new energy electric automobiles can be broken through, the resource utilization rate is improved, the environmental pollution is reduced, and the method has very important significance. Aiming at the characteristic that elements of nickel, cobalt and manganese are matched in a manganese nodule and a nickel, cobalt and manganese ternary cathode material, nickel, cobalt and manganese are separated from other impurity cations and purified from leachate of a manganese nodule reduction smelting alloy, a high-cost and high-pollution nickel, cobalt and manganese extraction separation process is not needed, the concentration of nickel, cobalt and manganese metal ions is adjusted, and a nickel, cobalt and manganese ternary cathode material precursor is prepared through coprecipitation. The obtained precursor nickel cobalt manganese hydroxide of the ternary cathode material can be further sintered to obtain the ternary cathode material nickel cobalt manganese oxide.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a method for preparing a nickel-cobalt-manganese ternary cathode material precursor by carrying out reduction smelting on manganese nodules to obtain a molten nickel-cobalt-manganese-copper-iron alloy, preparing alloy powder by spraying powder, obtaining a mixed solution containing nickel, cobalt, manganese and copper ions by adopting a synergistic oxidation selective leaching technology, obtaining a high-purity nickel, cobalt and manganese mixed solution after deep purification and impurity removal, and preparing a nickel-cobalt-manganese ternary cathode material precursor by adopting a coprecipitation process. Aiming at the matching of nickel-cobalt-manganese elements in manganese nodules and nickel-cobalt-manganese elements in a nickel-cobalt-manganese ternary positive electrode material precursor, impurity elements are separated through selective leaching, a nickel-cobalt-manganese solution is purified and purified deeply, a high-cost and high-pollution nickel-cobalt-manganese extraction separation process is not needed, the nickel-cobalt-manganese ternary positive electrode material precursor prepared through a coprecipitation method is short in process, high in added value of products, and good in industrial prospect.
2. The invention provides a method for preparing a nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules, provides a method for preparing the nickel-cobalt-manganese ternary positive electrode material precursor with high efficiency, short flow and high product added value, solves the problem of serious shortage of nickel-cobalt resources, improves the resource utilization rate, reduces the environmental pollution, realizes the clean high-value utilization of non-ferrous metal resources, and can further break through the resource bottleneck of new energy electric vehicles.
3. The first discharge capacity of the nickel-cobalt-manganese ternary cathode material prepared by the invention is not lower than 170 mA.g < -1 > under the voltage of 3.0-4.2V and 0.1C, and the discharge capacity retention rate is more than 90% after 100 cycles, which shows that the nickel-cobalt-manganese ternary cathode material prepared by the precursor and the lithium source has high discharge capacity and stable discharge. Therefore, the nickel-cobalt-manganese ternary cathode material precursor meets the preparation requirement of the cathode material, and the product has a good industrial application prospect.
Drawings
FIG. 1 is a photograph of a manganese nodule provided in example 1 of the present invention.
Fig. 2 is an SEM image of the nickel-cobalt-manganese ternary positive electrode material precursor 523 according to embodiment 1 of the present invention.
Fig. 3 is an SEM image of the nickel-cobalt-manganese ternary positive electrode material precursor 622 of example 2 of the present invention.
Fig. 4 is an SEM image of the nickel-cobalt-manganese ternary positive electrode material precursor 811 according to example 3 of the present invention.
Fig. 5 is a charge-discharge curve diagram of the nickel-cobalt-manganese ternary positive electrode material 523 in embodiment 1 of the present invention.
Fig. 6 is a charge-discharge curve diagram of the nickel-cobalt-manganese ternary cathode material 622 in embodiment 2 of the present invention.
Fig. 7 is a charge-discharge curve diagram of the nickel-cobalt-manganese ternary positive electrode material 811 according to embodiment 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The embodiment comprises the following steps:
1.1 crushing 1kg of manganese nodule to-60 meshes, drying until the moisture content is 5.1wt%, and mixing the crushed and dried manganese nodule, coke, quartz and quicklime to obtain a mixed material; in the mixed material, the mass percentage isWherein the coke accounts for 10%, the quartz accounts for 3%, the quicklime accounts for 4%, and the manganese nodule after crushing and drying accounts for 83%; CaO in quicklime/SiO in quartz2Mass ratio of<1.5；
1.2 reducing and smelting the mixed material obtained in the step (1) at 1300 ℃ for 30min to obtain molten nickel, cobalt, manganese, iron and copper (a small amount of alloy), and discarding slag; the alloy yield is 10.86%, and the manganese nodule as the raw material and the alloy components obtained in the step (wt%):
1.3 adding the molten nickel, cobalt, manganese, iron and copper alloy obtained in the step 2 into an atomization powder making device, making powder by high-pressure nitrogen gas spraying, and controlling the particle size of the powder to be less than or equal to 100 meshes to obtain alloy powder; the pressure of the used nitrogen is 0.8 MPa;
1.4 selective leaching of alloy powder: adding catalyst ammonium sulfate into a sulfuric acid solution (the concentration of the sulfuric acid solution is 4 mol/L), heating to 70 ℃, preserving heat, continuously introducing ozone (the introduction amount is 0.5L/min), adding the alloy powder obtained in the step (3) (the mass ratio of the alloy powder to the sulfuric acid solution is 1: 6), and stirring for 6 hours at the stirring speed of 500 r/min; the amount of ammonium sulfate used was 10 g/(L sulfuric acid solution).
1.5 under the condition of keeping stirring in the step (4), introducing hydrogen peroxide in the step (4), cooperating with ozone for oxidation leaching, controlling the pH value at the end point of the reaction to be 3, and carrying out solid-liquid separation after the reaction is carried out for 2 hours to obtain iron slag and leachate containing nickel, cobalt, manganese and copper;
the volume of the hydrogen peroxide solution is 10 percent of the volume of the raw sulfuric acid solution in the step (4). (the concentration of hydrogen peroxide is preferably 80 g/l); the stirring speed is 1500 r/min.
The components of the leaching solution are as follows (g/L):
1.6 adding MnS into the leachate containing nickel, cobalt, manganese and copper obtained in the step (5) for deep Cu removal, and performing solid-liquid separation to obtain an acidic leachate containing Ni, Co and Mn;
the mol ratio of MnS to Cu in the leaching solution containing nickel, cobalt, manganese and copper is 1.4: 1;
solution Cu after deep Cu removal2+0.002 g/L;
1.7, adding NaF into the acidic leaching solution containing Ni, Co and Mn obtained in the step (6), deeply removing Ca and Mg, and carrying out solid-liquid separation to obtain a high-purity acidic solution containing Ni, Co and Mn;
the ratio of NaF to the sum of the amounts of Ca and Mg in the acid leaching solution containing Ni, Co and Mn is 3: 1.
Ca after deep purification2+0.001g/L, Mg2+0.002 g/L;
1.8 adopting NaOH solution to adjust the pH value of the high-purity acid solution containing Ni, Co and Mn obtained in the step (7) to 5, and removing Ni from the solution2+、Co2+、Mn2+Precipitating all other cations with sodium hydroxide, and filtering to obtain a mixed solution A;
1.9 regulating the molar ratio of nickel, cobalt and manganese in the mixed solution A to 0.5 by using a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution: 0.2: 0.3, and adjusting the pH value to 5 by adopting a sodium hydroxide solution or a sulfuric acid solution to obtain a mixed solution B; the total molar concentration of nickel, cobalt and manganese elements in the mixed solution B is 1.5 mol/L.
1.10 adding ammonia water A, a sodium hydroxide solution and the mixed solution B obtained in the step (9) into a reactor filled with a base solution at the same time to obtain a mixture C, continuously stirring for 10 hours at the temperature of 30 ℃ under the protection of a nitrogen atmosphere for precipitation reaction, and obtaining a nickel-cobalt-manganese mixed precipitate after the precipitation is finished; the concentration of the ammonia water A is 0.4 mol/L;
in the mixture C, the mol ratio of the ammonium ions, the sodium hydroxide and the nickel-cobalt-manganese element is 0.4: 1.8: 1.
the base solution is prepared by dissolving ammonia B and sodium hydroxide in deionized water, the pH value of the base solution is 10, and the molar ratio of ammonium ions to sodium hydroxide in the base solution is 0.5: 1. the volume of the base solution is 5% of the volume of the mixed solution B.
1.11 adding a sodium hydroxide solution with the mass concentration of 12% into the nickel-cobalt-manganese mixed precipitate, wherein the liquid-solid mass ratio of the sodium hydroxide solution to the nickel-cobalt-manganese mixed precipitate is 10:1, uniformly stirring, aging at 30 ℃ for 0.5h, and after the aging, sequentially washing, filtering and vacuum drying to finally obtain the nickel-cobalt-manganese ternary cathode material precursor. The vacuum drying temperature is 80 ℃, the time is 5 hours, and the moisture content of the dry powder is 0.19 wt%.
Precursor Ni of nickel-cobalt-manganese ternary cathode material prepared by the embodiment0.5Co0.2Mn0.3(OH)2The particle size of D50 is 5.8 μm, the tap density is 2.25g/mL, the molar ratio of nickel, cobalt and manganese elements is 0.510:0.208:0.298, and an electrochemical test shows that the precursor Ni of the nickel, cobalt and manganese ternary cathode material prepared in the embodiment is Ni0.5Co0.2Mn0.3(OH)2The nickel-cobalt-manganese ternary positive electrode material prepared by mixing and sintering lithium carbonate has a voltage platform of 3.0-4.0V, and the first discharge capacity of the positive electrode material is 171 mA-g at 0.1C-1And after the cycle of 100 weeks, the discharge capacity retention rate is more than 90%, which shows that the discharge capacity of the nickel-cobalt-manganese ternary cathode material precursor prepared by the method and the cathode material prepared by the lithium source is high and the discharge is stable. Therefore, the nickel-cobalt-manganese ternary cathode material precursor meets the preparation requirement of the cathode material.
Example 2
The embodiment comprises the following steps:
2.1 crushing 1kg of manganese nodule to-60 meshes, drying until the water content is 9.8wt%, and mixing the crushed and dried manganese nodule, coke, quartz and quicklime to obtain a mixed material; in the mixed material, the coke accounts for 8 percent, the quartz accounts for 5 percent, the quicklime accounts for 6 percent, and the rest is crushed and dried manganese nodule, CaO in the quicklime/SiO in the quartz2Mass ratio of<1.5；
2.2 reducing and smelting the mixed material obtained in the step (1) at 1400 ℃ for 90min to obtain molten nickel, cobalt, manganese, iron and copper (a small amount of) alloy, and discarding slag; the alloy yield is 11.24%, and the manganese nodule and the obtained alloy components (wt%):
2.3 adding the molten nickel, cobalt, manganese, iron and copper alloy obtained in the step (2) into an atomization powder making device, making powder by high-pressure nitrogen gas spraying, and controlling the particle size of the powder to be less than or equal to 100 meshes to obtain alloy powder; the pressure of the nitrogen is 1.5MPa,
2.4 selective leaching of alloy powder: adding catalyst ammonium sulfate into a sulfuric acid solution (the concentration of the sulfuric acid solution is 4 mol/L), heating to 80 ℃, preserving heat, continuously introducing ozone, adding the alloy powder obtained in the step (3) (the mass ratio of the alloy powder to the sulfuric acid solution is 1: 8), and stirring for 4 hours at the stirring speed of 1000 r/min; the amount of ammonium sulfate used was 40 g/(L sulfuric acid solution). In the step, the precipitate obtained by selective leaching of the alloy powder contains almost all elements such as Fe, tungsten and the like in the raw material, and Fe and tungsten in the leaching solution are trace.
The flow rate of the ozone is 1.0L/min.
2.5 under the condition of keeping stirring in the step (4), introducing hydrogen peroxide into the step (4), cooperating with ozone for oxidation leaching, controlling the pH value at the end point of the reaction to be 4.5, and carrying out solid-liquid separation after 6 hours of reaction to obtain iron slag and leachate containing nickel, cobalt, manganese and copper; the volume of the hydrogen peroxide solution is 30 percent of the volume of the raw sulfuric acid solution in the step (4). (the concentration of hydrogen peroxide is 40 g/l)
The stirring speed is 1500 r/min.
The components of the leaching solution are as follows (g/L):
2.6 adding MnS into the leachate containing nickel, cobalt, manganese and copper obtained in the step 5 to deeply remove Cu, and performing solid-liquid separation to obtain an acidic leachate containing Ni, Co and Mn;
the mol ratio of MnS to Cu in the leaching solution containing nickel, cobalt, manganese and copper is 1.4: 1;
the Cu2+ of the solution after deep Cu removal is 0.002 g/L;
2.7, adding NaF into the acidic leaching solution containing Ni, Co and Mn obtained in the step (6), deeply removing Ca and Mg, and carrying out solid-liquid separation to obtain a high-purity acidic solution containing Ni, Co and Mn;
the ratio of NaF to the sum of the amounts of Ca and Mg in the acid leaching solution containing Ni, Co and Mn is 3: 1.
Ca after deep purification2+0.001g/L, Mg2+0.002 g/L;
2.8 adopting NaOH solution to adjust the pH value of the acid leaching solution of Ni, Co and Mn to 5.5, removing Ni in the solution2+、Co2+And cations except Mn2+ and sodium hydroxide generate precipitates, and a mixed solution A is obtained after filtration;
2.9 adjusting the molar ratio of nickel, cobalt and manganese in the mixed solution A obtained in the step (8) to 0.6 by using a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution: 0.2: 0.2, and adjusting the pH value to 5.5 by adopting a sodium hydroxide solution or a sulfuric acid solution to obtain a mixed solution B; the total molar concentration of nickel, cobalt and manganese elements in the mixed solution B is 1.5 mol/L.
2.10 adding ammonia water A, a sodium hydroxide solution and the mixed solution B obtained in the step (9) into a reactor filled with a base solution at the same time to obtain a mixture C, continuously stirring for 14 hours at the temperature of 40 ℃ under the protection of a nitrogen atmosphere for precipitation reaction, and obtaining a nickel-cobalt-manganese mixed precipitate after the precipitation is finished; the concentration of the ammonia water A is 0.6 mol/L; in the mixture C, the mol ratio of the ammonium ions, the sodium hydroxide and the nickel-cobalt-manganese element is 0.8: 1.8: 1.
the base solution is prepared by dissolving ammonia B and sodium hydroxide in deionized water, the pH value of the base solution is 11, and the molar ratio of ammonium ions to sodium hydroxide in the base solution is 0.6: 1. the volume of the base solution is 8% of the volume of the mixed solution B.
2.11 adding a sodium hydroxide solution (the mass concentration of the sodium hydroxide is 12%, and the liquid-solid mass ratio of the sodium hydroxide solution to the nickel-cobalt-manganese mixed precipitate is 10: 1) into the nickel-cobalt-manganese mixed precipitate obtained in the step (10), uniformly stirring, aging at 40 ℃ for 2h, and after the aging is finished, sequentially washing, filtering and vacuum drying to finally obtain the nickel-cobalt-manganese ternary cathode material precursor. The vacuum drying temperature is 100 ℃, the time is 3 hours, and the moisture content of the dry powder is 0.1 wt%.
The particle size of D50 of the precursor Ni0.6Co0.2Mn0.2 Ni-Co-Mn ternary positive electrode material prepared in the embodiment is 6.4 μm, the tap density is 2.32g/mL, and the molar ratio of Ni, Co and Mn elements is 0.605:0.203: 0.199. electrochemical tests show that the voltage platform of the Ni-Co-Mn ternary positive electrode material prepared by mixing and sintering the precursor Ni0.6Co0.2Mn0.2 Ni-Co-Mn ternary positive electrode material prepared in the embodiment with lithium carbonate is 3.0V-4.2V, the discharge capacity of the positive electrode material is not lower than 178 mA-g-1 for the first time under 0.1C, and the discharge capacity retention rate is more than 92% after circulation for 100 times, which shows that the discharge capacity of the positive electrode material prepared by the precursor of the Ni-Co-Mn ternary positive electrode material prepared in the invention and a lithium source is high and stable in discharge. Therefore, the nickel-cobalt-manganese ternary cathode material precursor meets the preparation requirement of the cathode material.
Example 3
The embodiment comprises the following steps:
3.1 taking 1kg of manganese nodule, crushing the manganese nodule to minus 80 meshes, drying the manganese nodule until the moisture content is 9.8wt%, and mixing the crushed and dried manganese nodule, coke, quartz and quicklime to obtain a mixed material; in the mixed material, by mass percentage, the coke accounts for 8 percent, the quartz accounts for 5 percent, the quicklime accounts for 6 percent, and the rest is crushed and dried manganese nodule; CaO in quicklime/SiO in quartz2Mass ratio of<1.5；
3.2 reducing and smelting the mixed material obtained in the step (1) at 1600 ℃ for 120min to obtain molten nickel, cobalt, manganese, iron and copper (a small amount of) alloy, and discarding slag; the alloy yield is 11.56%, and the manganese nodule and the obtained alloy components are (%):
3.3 adding the molten nickel, cobalt, manganese, iron and copper alloy obtained in the step (2) into an atomization powder making device, making powder by high-pressure nitrogen gas spraying, and controlling the particle size of the powder to be less than or equal to 100 meshes to obtain alloy powder; the nitrogen pressure is 2.5 MPa;
3.4 selective leaching of alloy powder: adding catalyst ammonium sulfate into sulfuric acid solution (the concentration of the sulfuric acid solution is 3 mol/L), heating to 90 ℃, preserving heat, continuously introducing ozone, adding the alloy powder obtained in the step (3) (the mass ratio of the alloy powder to the sulfuric acid solution is 1: 12), and stirring for 6 hours; the amount of ammonium sulfate used was 80 g/(L sulfuric acid solution). In the step, the precipitate obtained by selective leaching of the alloy powder contains almost all elements such as Fe, tungsten and the like in the raw material, and Fe and tungsten in the leaching solution are trace.
The flow rate of the introduced ozone is 3L/min. The stirring speed was 1000 r/min.
3.5 under the condition of keeping stirring in the step (4), introducing hydrogen peroxide into the step (4), cooperating with ozone for oxidation leaching, controlling the pH value at the end point of the reaction to be 4.5, and carrying out solid-liquid separation after 4 hours of reaction to obtain iron slag and leachate containing nickel, cobalt, manganese and copper; the stirring speed was 500 r/min. The volume of the hydrogen peroxide solution is 30 percent of the volume of the raw sulfuric acid solution in the step (4). (Hydrogen peroxide concentration of 50 g/l)
The components of the leaching solution are as follows (g/L):
3.6 adding MnS into the leachate containing nickel, cobalt and manganese to deeply remove Cu, carrying out solid-liquid separation to obtain an acidic leachate containing Ni, Co and Mn, and obtaining a solution Cu after deeply removing Cu2+0.003 g/L; the mol ratio of MnS to Cu in the leaching solution containing nickel, cobalt, manganese and copper is 1.2: 1;
3.7 adding NaF into the acid mixed solution to deeply remove Ca and Mg, carrying out solid-liquid separation to obtain high-purity acid solution containing Ni, Co and Mn, and deeply purifying Ca2+0.002g/L of Mg2+0.003 g/L; the ratio of NaF to the sum of the amounts of Ca and Mg in the acid leaching solution containing Ni, Co and Mn is 3: 1.
3.8, adjusting the pH value of the acidic leaching solution of Ni, Co and Mn to 6 by adopting NaOH solution, generating precipitates by cations except Ni2+, Co2+ and Mn2+ and sodium hydroxide in the solution, and filtering to obtain a mixed solution A;
3.9 adjusting the molar ratio of nickel, cobalt and manganese in the mixed solution A obtained in the step (8) to 0.8 by using a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution: 0.1: 0.1, and adjusting the pH value to 5.5 by adopting a sodium hydroxide solution or a sulfuric acid solution to obtain a mixed solution B; the total molar concentration of nickel, cobalt and manganese elements in the mixed solution B is 2.0 mol/L.
3.10 adding ammonia water A, a sodium hydroxide solution and the mixed solution B obtained in the step (9) into a reactor filled with a base solution at the same time to obtain a mixture C, continuously stirring for 18 hours at the temperature of 60 ℃ under the protection of a nitrogen atmosphere for precipitation reaction, and obtaining a nickel-cobalt-manganese mixed precipitate after the precipitation is finished; the concentration of the ammonia water A is 0.8 mol/L; in the mixture C, the mol ratio of the ammonium ions, the sodium hydroxide and the nickel-cobalt-manganese element is 0.4: 2.2: 1.
the base solution is prepared by dissolving ammonia B and sodium hydroxide in deionized water, the pH of the base solution is 12, and the molar ratio of ammonium ions to sodium hydroxide in the base solution is 1.5: 1. the volume of the base solution is 10% of the volume of the mixed solution B.
3.11 adding a sodium hydroxide solution (the mass concentration of the sodium hydroxide is 12%, and the liquid-solid mass ratio of the sodium hydroxide solution to the nickel-cobalt-manganese mixed precipitate is 15: 1) into the nickel-cobalt-manganese mixed precipitate obtained in the step (10), uniformly stirring, aging at 60 ℃ for 2h, and after the aging is finished, sequentially washing, filtering and vacuum drying to finally obtain the nickel-cobalt-manganese ternary cathode material precursor. The vacuum drying temperature is 110 ℃, the time is 2h, and the moisture content of the dry powder is 0.18 wt%.
The particle size of D50 of the precursor of the nickel-cobalt-manganese ternary positive electrode material prepared in the embodiment is 7.2 mu m, the tap density is 2.41g/mL, and the molar ratio of nickel, cobalt and manganese elements is 0.795:0.104: 0.102. electrochemical tests show that the voltage platform of the nickel-cobalt-manganese ternary positive electrode material prepared by mixing the precursor of the nickel-cobalt-manganese ternary positive electrode material prepared in the embodiment with lithium hydroxide is 3.0V-4.2V, the first discharge capacity of the positive electrode material is not lower than 196mA · g-1 at 0.1C, and after 100 cycles, the discharge capacity retention rate is more than 93%, which shows that the discharge capacity of the positive electrode material prepared by the precursor of the nickel-cobalt-manganese ternary positive electrode material and a lithium source is high and the discharge is stable. Therefore, the nickel-cobalt-manganese ternary cathode material precursor meets the preparation requirement of the cathode material.
Claims (9)
1. A method for preparing a nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules is characterized by comprising the following steps:
(1) crushing and drying the manganese nodules; mixing the crushed and dried manganese nodules, coke, quartz and quicklime to obtain a mixed material; in the mixed material, coke accounts for 5-20% of the total mass of the mixed material, quartz accounts for 3-10% of the total mass of the mixed material, crushed and dried manganese nodules account for 60-85% of the total mass of the mixed material, quicklime accounts for 5-10% of the total mass of the mixed material, and CaO in the quicklime/SiO in the quartz2Mass ratio of<1.5；
(2) Reducing and smelting the mixed material obtained in the step (1) at the temperature of 1300-1600 ℃ to obtain molten nickel, cobalt, manganese, iron and copper alloy, and discarding slag;
(3) adding the molten nickel, cobalt, manganese, iron and copper alloy obtained in the step (2) into an atomization powder making device, and making powder by high-pressure nitrogen gas spraying, wherein the particle size of the powder is controlled to be less than or equal to 100 meshes, so as to obtain alloy powder;
(4) selective leaching of alloy powder: adding catalyst ammonium sulfate into sulfuric acid solution, heating to 70-90 ℃, preserving heat, continuously introducing ozone, adding the alloy powder obtained in the step (3), and stirring for 2-6 hours;
(5) under the condition of keeping stirring in the step (4), introducing hydrogen peroxide into the step (4), cooperating with ozone for oxidation leaching, controlling the pH value at the end point of the reaction to be 3-5, and carrying out solid-liquid separation after the reaction is carried out for 2-6h to obtain iron slag and leachate containing nickel, cobalt, manganese and copper;
(6) adding MnS into the leachate containing nickel, cobalt, manganese and copper obtained in the step (5) to deeply remove Cu, and performing solid-liquid separation to obtain an acidic leachate containing Ni, Co and Mn;
the mol ratio of MnS to Cu in the leaching solution containing nickel, cobalt, manganese and copper is 1-1.6: 1;
(7) adding NaF into the acidic leaching solution containing Ni, Co and Mn obtained in the step (6), deeply removing Ca and Mg, and carrying out solid-liquid separation to obtain a high-purity acidic solution containing Ni, Co and Mn;
the ratio of NaF to the sum of the amounts of Ca and Mg in the acid leaching solution containing Ni, Co and Mn is 2-3: 1;
(8) adjusting the pH value of the high-purity acidic solution containing Ni, Co and Mn obtained in the step (7) to 5-6 by adopting NaOH solution, and removing Ni from the solution2+、Co2+、Mn2+Precipitating all other cations with sodium hydroxide, and filtering to obtain a mixed solution A;
(9) adjusting the molar ratio of nickel, cobalt and manganese in the mixed solution A obtained in the step (8) to (0.4-0.9) by using nickel sulfate, cobalt sulfate and manganese sulfate: (0.05-0.4): (0.05-0.4), and adjusting the pH to 5-6 by adopting a sodium hydroxide solution or a sulfuric acid solution to obtain a mixed solution B;
(10) adding ammonia water A, a sodium hydroxide solution and the mixed solution B obtained in the step (9) into a reactor filled with a base solution at the same time to obtain a mixture C, continuously stirring for 10-18h at the temperature of 30-60 ℃ under the protection of a nitrogen atmosphere for precipitation reaction, and obtaining a nickel-cobalt-manganese mixed precipitate after the precipitation is finished; the concentration of the ammonia water A is 0.4-0.8 mol/L; the base solution is prepared by dissolving ammonia B and sodium hydroxide in deionized water, the pH value of the base solution is 10-12, and the molar ratio of ammonium ions to sodium hydroxide in the base solution is (0.5-1.5): 1; the volume of the base solution is 5-10% of the volume of the mixed solution B;
(11) and (3) adding a sodium hydroxide solution into the nickel-cobalt-manganese mixed precipitate obtained in the step (10), uniformly stirring, aging at the temperature of 30-70 ℃ for 0.5-2h, and washing, filtering and vacuum drying sequentially after aging to finally obtain the nickel-cobalt-manganese ternary cathode material precursor.
2. The method for preparing the nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodules according to claim 1, wherein in the step (1), the crushing refers to crushing the manganese nodules to a particle size of less than or equal to 60 meshes; the drying means drying the crushed manganese nodules until the moisture content is less than or equal to 15% by mass.
3. The method for preparing the nickel-cobalt-manganese ternary cathode material precursor by using the manganese nodule as the precursor in the claim 1 or 2, wherein in the step (2), the reduction smelting time is 30-120 min; in the step (3), the pressure of the high-pressure nitrogen is 0.8-2.5 MPa.
4. The method for preparing the nickel-cobalt-manganese ternary cathode material precursor by using the manganese nodule as the precursor in the claim 1 or 2, wherein in the step (4), the amount of the ammonium sulfate is 10-80g/L sulfuric acid solution; the flow rate of the introduced ozone is 0.5-3L/min.
5. The method for preparing the nickel-cobalt-manganese ternary cathode material precursor by using the manganese nodule as claimed in claim 1 or 2, wherein in the step (5), the volume of the added hydrogen peroxide is 10-50% of the volume of the raw sulfuric acid solution in the step (4).
6. The method for preparing the nickel-cobalt-manganese ternary positive electrode material precursor by using the manganese nodule as the main component in the claim 1 or 2, wherein in the step (6), Cu is contained in the acidic leaching solution containing Ni, Co and Mn2+The concentration is less than or equal to 0.004 g/L; in the step (7), Ca is contained in high-purity acid solution containing Ni, Co and Mn2+Concentration is less than or equal to 0.004g/L, Mg2+The concentration is less than or equal to 0.004 g/L.
7. The method for preparing the nickel-cobalt-manganese ternary cathode material precursor from the manganese nodule as claimed in claim 1 or 2, wherein in the step (9), the total molar concentration of the nickel, cobalt and manganese elements in the mixed solution B is 0.8mol/L-2.0 mol/L.
8. The method for preparing the nickel-cobalt-manganese ternary positive electrode material precursor from the manganese nodule according to claim 1 or 2, wherein in the step (10), the molar ratio of the ammonium ion, the sodium hydroxide and the sum of nickel-cobalt-manganese elements in the mixture C is (0.4-0.8): (1.8-2.2): 1.
9. the method for preparing the nickel-cobalt-manganese ternary cathode material precursor by using the manganese nodule as the precursor in the step (11), wherein the vacuum drying temperature is 80-110 ℃, the vacuum drying time is 2-5h, and the moisture content after drying is less than or equal to 1.0 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910040438.5A CN109921008B (en) | 2019-01-16 | 2019-01-16 | Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910040438.5A CN109921008B (en) | 2019-01-16 | 2019-01-16 | Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109921008A CN109921008A (en) | 2019-06-21 |
| CN109921008B true CN109921008B (en) | 2020-08-18 |
Family
ID=66960404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910040438.5A Active CN109921008B (en) | 2019-01-16 | 2019-01-16 | Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109921008B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111192762B (en) * | 2020-01-23 | 2021-07-20 | 上海应用技术大学 | Cu-Co-P composite material and preparation method and application thereof |
| CN112661201B (en) * | 2020-12-23 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for preparing nickel cobalt lithium manganate through reverse positioning of power battery and application |
| CN113060712B (en) * | 2021-03-15 | 2023-01-17 | 中南大学 | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder |
| CN115584400B (en) * | 2022-09-23 | 2024-01-09 | 广东邦普循环科技有限公司 | Feeding method of nickel-cobalt-manganese metal liquid |
| CN115784324B (en) * | 2022-11-29 | 2024-04-12 | 四川蜀矿环锂科技有限公司 | Method for recycling and preparing ternary positive electrode material precursor by using waste ternary lithium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010126779A (en) * | 2008-11-28 | 2010-06-10 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel concentrate from used nickel hydride battery |
| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN105858724A (en) * | 2016-05-16 | 2016-08-17 | 中南大学 | Method of using solution atomization method to prepare superfine Sb oxide |
| CN107230811A (en) * | 2016-03-25 | 2017-10-03 | 中国科学院过程工程研究所 | The Selectively leaching agent of metal component and recovery method in a kind of positive electrode |
| CN108987741A (en) * | 2018-06-12 | 2018-12-11 | 西安理工大学 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof |
-
2019
- 2019-01-16 CN CN201910040438.5A patent/CN109921008B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010126779A (en) * | 2008-11-28 | 2010-06-10 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel concentrate from used nickel hydride battery |
| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN107230811A (en) * | 2016-03-25 | 2017-10-03 | 中国科学院过程工程研究所 | The Selectively leaching agent of metal component and recovery method in a kind of positive electrode |
| CN105858724A (en) * | 2016-05-16 | 2016-08-17 | 中南大学 | Method of using solution atomization method to prepare superfine Sb oxide |
| CN108987741A (en) * | 2018-06-12 | 2018-12-11 | 西安理工大学 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109921008A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109921008B (en) | Method for preparing nickel-cobalt-manganese ternary positive electrode material precursor by using manganese nodule | |
| CN108878866B (en) | Method for preparing ternary material precursor and recovering lithium by using ternary cathode material of waste lithium ion battery | |
| CN111534697A (en) | Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries | |
| CN101875129B (en) | Method for comprehensive utilization of high-iron bauxite | |
| CN113060712B (en) | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder | |
| CN103614571A (en) | Combined leaching process of laterite-nickel ore | |
| CN101230422A (en) | Method for enriching nickel from lateritic nickel with co-production of iron-oxide red | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| WO2012171481A1 (en) | Hydrometallurgical process for complete and comprehensive recovery with substantially no wastes and zero emissions | |
| CN203530398U (en) | Laterite-nickel ore jointly leaches system | |
| CN111254276A (en) | Method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of sodium reduction roasting | |
| CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| CN113416843A (en) | Superfine grinding-oxygen pressure leaching process for nickel sulfide concentrate | |
| CN112877545A (en) | Method for recycling nickel, cobalt and iron by cooperatively treating waste nickel-hydrogen batteries through nickel smelting slag | |
| Luo et al. | Self-driven and efficient leaching of limonitic laterite with phosphoric acid | |
| CN111057847A (en) | Green method for preparing battery-grade nickel sulfate from nickel salt | |
| CN115058605A (en) | Method for recovering waste lithium battery material | |
| CN112725621B (en) | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method | |
| CN115074540B (en) | Comprehensive recovery method for valuable components of waste power battery | |
| CN212925126U (en) | Selection and smelting combined comprehensive recovery device for waste lithium ion batteries | |
| CN112646976B (en) | Method for synergistically leaching nickel, cobalt and manganese by utilizing waste lithium ion battery black powder and nickel cobalt sulfide ore and application | |
| CN115505727A (en) | Process method for treating waste nickel-cobalt-manganese ternary lithium battery oxide | |
| CN114086004A (en) | Method for selectively and efficiently extracting manganese from manganese-rich slag | |
| CN114614136A (en) | Method for preparing ferric phosphate dihydrate and ternary cathode material from laterite-nickel ore | |
| CN112777642A (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200512 Address after: 311811 No.92, Hongcheng Road, Taozhu street, Zhuji City, Shaoxing City, Zhejiang Province Applicant after: ZHEJIANG PAWA NEW ENERGY Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 154 Applicant before: CENTRAL SOUTH University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |