CN115959656A - Method for producing graphite negative electrode material of lithium electronic battery by adopting aluminum electrolysis waste cathode - Google Patents
Method for producing graphite negative electrode material of lithium electronic battery by adopting aluminum electrolysis waste cathode Download PDFInfo
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Abstract
The application provides a method for producing a graphite cathode material of a lithium electronic battery by adopting an aluminum electrolysis waste cathode, and relates to the technical field of comprehensive utilization of aluminum electrolysis solid waste resources. The method for producing the graphite cathode material of the lithium electronic battery by adopting the aluminum electrolysis waste cathode comprises the following steps: carrying out coarse crushing and first grinding on the aluminum electrolysis waste cathode carbon blocks to obtain micro powder, and mixing the micro powder, asphalt, natural graphite granulation tailings and a solvent for coating to obtain a sphere-like coating material; roasting and graphitizing the quasi-spherical coating material, and performing secondary grinding and multi-level wind classification on the cooled material to obtain the graphite cathode material of the lithium ion battery with different particle levels. According to the method for producing the graphite cathode material of the lithium electronic battery by adopting the aluminum electrolysis waste cathode, the aluminum electrolysis waste cathode and the low-value spherical graphite tailing are used as raw materials, the lithium ion battery cathode material with excellent performance and high added value is obtained, and high-quality utilization of hazardous waste and spherical graphite tailing is realized.
Description
Technical Field
The application relates to the technical field of comprehensive utilization of aluminum electrolysis solid waste resources, in particular to a method for producing a graphite cathode material of a lithium electronic battery by adopting an aluminum electrolysis waste cathode.
Background
The waste cathode of the electrolytic aluminum is an important component of the overhaul residue. The spent cathode carbon block is composed of about 65% carbon and about 35% fluoride, and further contains a small amount of silicate and cyanide. The most significant environmental hazard of spent cathodes is derived from fluorine. Because the electrolytic aluminum waste cathode works in a high-temperature environment for a long time, the carbon in the electrolytic aluminum waste cathode is highly graphitized, and the recovery value is very high. Therefore, the waste cathode is defined as dangerous waste and has strong resource.
At present, most domestic enterprises adopt landfill or stockpiling to treat, so that harmless treatment and resource utilization of the waste cathode cannot be realized, and components such as sodium fluoride, aluminum fluoride, cryolite and the like in the waste cathode permeate into soil along with rainwater, so that the environment is seriously harmed, and fluorine pollution is caused; some enterprises adopt a combustion method, but secondary pollution caused by fluoride is difficult to meet the requirement of environmental protection. The aluminum electrolysis enterprises urgently need applicable waste cathode harmless disposal and resource utilization technologies.
Aiming at the harmless and resource treatment technology of the waste cathode, researchers develop a great deal of research, and related technologies mainly comprise wet harmless treatment, flotation-sulfuric acid combined treatment, rotary kiln fire treatment, high-temperature volatilization-graphitization treatment and the like. The wet harmless treatment only dissolves out fluoride in the waste cathode and carries out harmless treatment, and the resource utilization of carbon cannot be realized; although the flotation-sulfuric acid combined treatment can collect carbon components and further adopts sulfuric acid and the like for purification, the treatment amount of wastewater is large, and partial dangerous waste residues are generated, so that high-value utilization of the carbon components cannot be realized; the carbon component in the waste cathode carbon block is burnt and removed by the rotary kiln pyrogenic process, part of fluoride is volatilized, the produced roasting slag is subjected to harmless landfill or is used in the building material industry such as cement, the fluoride returns to an electrolytic aluminum system and the like, the carbon emission of the technology is high, the resource utilization of the carbon cannot be realized, and the fluoride volatilization rate is not high, so that the contents of fluorine and sodium in the roasting slag are high; the high-temperature volatilization-graphitization process adopts a high-temperature one-step separation mode to obtain carbon products and fluoride products with high carbon content and high graphitization degree, and industrial demonstration has been developed.
The current waste cathode treatment process has low added value of products and does not realize harmless treatment and resource utilization.
Disclosure of Invention
The application aims to provide a method for producing a graphite negative electrode material of a lithium electronic battery by using an aluminum electrolysis waste cathode so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for producing graphite cathode materials of lithium electronic batteries by using aluminum electrolysis waste cathodes comprises the following steps:
carrying out coarse crushing and first grinding on the aluminum electrolysis waste cathode carbon blocks to obtain micro powder, and mixing the micro powder, asphalt, natural graphite granulation tailings and a solvent for coating to obtain a sphere-like coating material;
roasting and graphitizing the quasi-spherical coating material, and performing secondary grinding and multi-level wind classification on the cooled material to obtain the graphite cathode material of the lithium ion battery with different particle levels.
Preferably, the coarse crushing is carried out by a two-stage impact crusher, and the particle size of the obtained particles is less than or equal to 50mm.
Preferably, in the process of the treatment of the secondary impact crusher, the feeding granularity of the first stage is less than or equal to 500mm, and the discharging granularity is less than or equal to 100mm;
preferably, the materials of the impact plate and the hammer head of the secondary impact crusher are nodular cast iron with magnetism.
Preferably, the first grinding is performed by a vertical mill and an air classifier, and magnetic separation and iron removal are performed after the first grinding is completed, so that the particle size of the obtained micro powder is 5-50 μm.
Preferably, the solvent comprises mineral spirits and/or white oil;
preferably, the mass ratio of the micro powder, the asphalt, the natural graphite pelletizing tailings and the solvent is 10: (0.6-1.5): (1-2): (0.2-0.4), preferably 10;
preferably, the mineral spirits are No. 260.
Preferably, the coating temperature is 120-250 ℃, preferably 150 ℃, and the time is 2-5h;
preferably, the coating is performed using a kneader or a reaction vessel having a heating function.
Preferably, the temperature for roasting graphitization is 2400-3000 ℃, and the time is 8-20h; preferably 2800 deg.C for 12h.
Preferably, the roasting graphitization is performed by using an Acheson furnace or a series graphitization furnace, and the Acheson furnace or the series graphitization furnace is provided with a flue gas discharge system.
Preferably, the second grinding is performed by a vertical grinding machine, and the surfaces of a grinding disc and a grinding roller of the vertical grinding machine are made of hemispherical silicon carbide wear-resistant materials.
Preferably, the fractionation of the multi-stage air classification is 3-6 stages, preferably 5 stages.
Compared with the prior art, the beneficial effect of this application includes:
according to the method for producing the graphite cathode material of the lithium electronic battery by adopting the aluminum electrolysis waste cathode, the graphite cathode material of the lithium electronic battery with different grain grades is obtained through coarse crushing, first grinding, coating, roasting graphitization, second grinding and multi-stage wind classification; the aluminum electrolysis waste cathode and the low-value spherical graphite tailing are used as raw materials, the lithium ion battery cathode material with excellent performance and high added value is obtained, and high-quality utilization of hazardous waste and spherical graphite tailing is realized.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic view of a main structure of a vertical mill provided in the present application;
FIG. 2 is a schematic side view of a structural body of a vertical mill provided by the present application;
FIG. 3 is a process flow diagram of a method for producing graphite-based negative electrode materials for lithium electronic batteries using aluminum electrolysis waste cathodes according to the present application;
fig. 4 is a schematic diagram of the grinding-classification process in the embodiment.
Reference numerals:
1-a feed pipe; 2-a middle shell; 3, grinding the roller; 4-a rocker arm; 5-grinding disc; 6-a frame; 7-discharging a bin; 8-a first reducer; 9-a hydraulic cylinder; 10-a motor; 11-a coupling; 12-a second reducer; 13-discharge outlet.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of … …" appears in a clause of the subject of the claims rather than immediately after the subject matter, it defines only the elements described in that clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the recited range should be interpreted to include ranges of "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g, 2.689g, and the like. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A method for producing graphite cathode materials of lithium electronic batteries by adopting aluminum electrolysis waste cathodes comprises the following steps:
carrying out coarse crushing and first grinding on the aluminum electrolysis waste cathode carbon blocks to obtain micro powder, and mixing the micro powder, asphalt, natural graphite granulation tailings and a solvent for coating to obtain a sphere-like coating material;
roasting and graphitizing the quasi-spherical coating material, and performing secondary grinding and multi-level wind classification on the cooled material to obtain the graphite cathode material of the lithium ion battery with different particle levels.
The spherical-like coating material obtained by coating is used for improving the tap density of the finally obtained negative electrode material, so that the electrical property of the negative electrode material is improved.
The solvent is mainly used for dissolving the asphalt so as to effectively coat the micro powder and the natural graphite pelletizing tailings.
In an alternative embodiment, the coarse crushing is carried out by a two-stage impact crusher, and the particle size of the obtained particles is less than or equal to 50mm.
In an alternative embodiment, during the treatment of the two-stage impact crusher, the feed particle size of the first stage is less than or equal to 500mm, and the discharge particle size is less than or equal to 100mm; the second stage takes the discharged material of the first stage as a feed material, and the particle size of the discharged particles of the second stage is less than or equal to 50mm.
In an alternative embodiment, the material of the impact plate and the hammer head of the secondary impact crusher is nodular cast iron with magnetism.
Parts of the impact plate, the hammer head and the like of the impact crusher, which are contacted with the waste cathode, adopt cast iron with strong magnetism, and the screen mesh, the screen surface and the like of the vibrating screen adopt steel plates or steel meshes with strong magnetism, so that stainless steel non-magnetic materials cannot be adopted.
In an optional embodiment, the first grinding is performed by a vertical mill and an air classifier, and magnetic separation and iron removal are performed after the first grinding is completed, so that the particle size of the obtained micro powder is 5-50 μm.
Alternatively, the particle size of the finally obtained micro powder can be any value between 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or 5-50 μm.
In an alternative embodiment, the solvent comprises mineral spirits and/or white oil;
in an optional embodiment, the mass ratio of the micro powder, the asphalt, the natural graphite pelletizing tailings and the solvent is 10: (0.6-1.5): (1-2): (0.2-0.4), preferably 10;
in an alternative embodiment, the mineral spirits are No. 260.
No. 260 solvent oil is preferably selected, and the solvent oil has the characteristics of low content of volatile organic compounds, environmental protection, strong dissolving performance, low price and the like.
Optionally, the micro powder, the asphalt, the natural graphite pelletizing tailings (note: the natural graphite pelletizing tailings refer to materials which are left after natural crystalline flake graphite is pelletized and are difficult to pelletize, the particle size is less than 5 μm, and the fixed carbon content is usually 88% -95%), and the solvent oil may have a mass ratio of 10:0.6:1:0.2, 10:1:1.5:0.3, 10:1.5:2:0.4 or 10: (0.6-1.5): (1-2): (0.2-0.4).
In an alternative embodiment, the temperature of the coating is 120 ℃ to 250 ℃, preferably 150 ℃, for 2 to 5 hours;
in an alternative embodiment, the coating is performed using a kneader or a reaction vessel with a heating function.
Optionally, the coating temperature may be any value between 120 ℃, 150 ℃, 200 ℃, 250 ℃ or between 120 ℃ and 250 ℃, and the coating time may be any value between 2h, 3h, 4h, 5h or between 2h and 5 h.
In an optional embodiment, the temperature for roasting graphitization is 2400-3000 ℃, and the time is 8-20h; preferably 2800 ℃ for 12h.
Optionally, the temperature for the calcination graphitization may be 2400 ℃, 2500 ℃, 2600 ℃, 2700 ℃, 2800 ℃, 2900 ℃, 3000 ℃ or 2400 ℃ to 3000 ℃, and the time may be 8h, 10h, 12h, 14h, 16h, 18h, 20h or 8 to 20 h.
In an alternative embodiment, the fired graphitization is performed using an Acheson furnace or a series graphitization furnace with a flue gas exhaust system.
The improvement and increase of the flue gas discharge system aim at that the high-temperature flue gas containing fluoride salt and silicate in the waste cathode can easily overflow the graphitization furnace; and cooling the flue gas containing fluoride salt and silicate, and collecting the flue gas.
In an optional embodiment, the second grinding is performed by using a vertical mill, and the surfaces of a grinding disc and a grinding roller of the vertical mill are made of hemispherical silicon carbide wear-resistant materials.
The application requires that the roller surface of the vertical mill adopts silicon carbide ceramics, which is different from the vertical mill used for cement raw materials and clinker in the cement industry.
In an alternative embodiment, the separation stage of the multi-stage wind power stage is 3-6 stages, preferably 5 stages.
The wind power is classified into 3-6 grades according to the lithium ion battery graphite cathode material
(GB/T24332019) standard produces anode materials of different size fractions.
Optionally, the separation and classification of the multi-stage wind power classification may be any of 3 stages, 4 stages, 5 stages and 6 stages.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The aluminum electrolysis waste cathode carbon blocks used in the embodiments and the comparative examples have the same components and all comprise the following components:
C：60～80％，F：5～12％，Na：5～15％，Al：0.5～5％，Si：0.5～2％。
first, a vertical mill used in the present application will be described, and as shown in fig. 1 and 2, the vertical mill includes a feed pipe 1, a middle casing 2, a grinding roller 3, a swing arm 4, a grinding table 5, a frame 6, a discharge bin 7, a first reduction gear 8, a hydraulic cylinder 9, a motor 10, a coupling 11, a second reduction gear 12, and a discharge port 13.
Example 1
As shown in fig. 3 and fig. 4, the present embodiment provides a method for producing graphite-based negative electrode material for lithium electronic battery by using aluminum electrolysis waste cathode, which specifically includes the following steps:
(1) The first-stage impact crusher adopts PF1315, the feeding granularity can reach 500mm, and the discharging granularity can be controlled to 100mm; the second-stage impact crusher adopts PF1007, the feeding granularity can be 100mm, and the discharging granularity can be controlled to 30mm; the materials of the impact plate and the hammer head are selected from magnetic nodular cast iron;
(2) The material with the thickness of 30mm enters a vertical mill of a ceramic roller surface, the vertical mill and an air classifier form a closed-loop system, the product is 5-30 mu m, and the roller surfaces of a grinding disc and a grinding roller of the vertical mill adopt silicon carbide ceramic; removing iron from the micro powder of 5-30 μm by strong magnetism;
(3) The mass ratio of 5-30 mu m micro powder to coal tar pitch, flake graphite balling tailings and No. 260 solvent oil is 10.0;
(4) Roasting the spheroidal micro powder by adopting a special series graphitizing furnace for 8 hours at the roasting temperature of 2600 ℃ (controlling the roasting temperature by supplying power), and then naturally cooling;
(5) And grinding the cooled graphite powder by using a vertical grinding machine with a hemispherical ceramic roller surface, and classifying by 5 grades to obtain 4 types of lithium ion battery cathode material products with the particle sizes of D50= (20 +/-2) mu m, D50= (17 +/-2) mu m, D50= (12 +/-2) mu m and D50= (10 +/-2) mu m respectively, wherein the first discharge specific capacitance is not less than 340 (mA.h)/g.
Example 2
The embodiment provides a method for producing a graphite cathode material of a lithium electronic battery by adopting an aluminum electrolysis waste cathode, which specifically comprises the following steps:
(1) The first-stage impact crusher adopts PF1315, the feeding granularity can reach 500mm, and the discharging granularity can be controlled to 100mm; the second-stage impact crusher adopts PF1007, the feeding granularity can be 100mm, and the discharging granularity can be controlled to 30mm; the materials of the impact plate and the hammer head are selected from ductile cast iron with magnetism;
(2) The material with the thickness of 30mm enters a vertical mill of a ceramic roller surface, the vertical mill and an air classifier form a closed-loop system, the product is 5-30 mu m, and the roller surfaces of a grinding disc and a grinding roller of the vertical mill adopt silicon carbide ceramic; removing iron from the micro powder of 5-30 μm by strong magnetism;
(3) The mass ratio of 5-30 mu m micro powder to coal tar pitch, flake graphite balling tailings and No. 260 solvent oil is 10.0;
(4) Roasting the spheroidal micro powder by adopting a special series graphitizing furnace for 12 hours at the roasting temperature of 2800 ℃, and then naturally cooling;
(5) And grinding the cooled graphite powder by using a vertical mill with a hemispherical ceramic roller surface, and classifying by 5 grades to obtain 4 types of lithium ion battery negative electrode material products with the particle sizes of D50= (22 +/-2) mu m, D50= (18 +/-2) mu m, D50= (14 +/-2) mu m, D50= (11 +/-2) mu m and D50= (7 +/-2) mu m respectively, wherein the first discharge specific capacitance is not less than 350 (mA.h)/g.
Example 3
The embodiment provides a method for producing a graphite cathode material of a lithium electronic battery by adopting an aluminum electrolysis waste cathode, which specifically comprises the following steps:
(1) The first-stage impact crusher adopts PF1315, the feeding granularity can reach 500mm, and the discharging granularity can be controlled to 100mm; the second-stage impact crusher adopts PF1007, the feeding granularity can be 100mm, and the discharging granularity can be controlled to 30mm; the materials of the impact plate and the hammer head are selected from magnetic nodular cast iron;
(2) The material with the thickness of 30mm enters a vertical mill with a ceramic roller surface, the vertical mill and an air classifier form a closed-loop system, the product is 5-30 mu m, and the roller surfaces of a grinding disc and a grinding roller of the 5 vertical mill adopt silicon carbide ceramic; removing iron from the micro powder of 5-30 mu m by strong magnetism;
(3) The mass ratio of 5-30 μm micro powder to coal tar pitch, flake graphite balling tailings and No. 260 solvent oil is 10;
(4) Roasting the spheroidal micro powder by adopting a special series graphitizing furnace for 12 hours at 2800 ℃, and then naturally cooling;
(5) And grinding the cooled graphite powder by using a vertical mill with a hemispherical ceramic roll surface, and classifying by 5 grades to obtain 4 grades of lithium ion battery cathode material products, wherein the particle sizes are respectively D50= (22 +/-2) mu m, D50= (18 +/-2) mu m, D50= (14 +/-2) mu m, D50= (11 +/-2) mu m and D50= (7 +/-2) mu m, and the first discharge specific capacitance is not less than 360 (mA.h)/g.
Example 4
The embodiment provides a method for producing a graphite cathode material of a lithium electronic battery by adopting an aluminum electrolysis waste cathode, which specifically comprises the following steps:
(1) The first-stage impact crusher adopts PF1315, the feeding granularity can reach 500mm, and the discharging granularity can be controlled to 100mm; the second-stage impact crusher adopts PF1007, the feeding granularity can be 100mm, and the discharging granularity can be controlled to 30mm; the materials of the impact plate and the hammer head are selected from magnetic nodular cast iron;
(2) The material with the thickness of 30mm enters a vertical mill with a ceramic roller surface, the vertical mill and an air classifier form a closed-loop system, the product is 5-30 mu m, and the roller surfaces of a grinding disc and a grinding roller of the 5 vertical mill adopt silicon carbide ceramic; removing iron from the micro powder of 5-30 μm by strong magnetism;
(3) The mass ratio of the micro powder with the particle size of 5-30 mu m to the coal tar pitch, the flake graphite balling tailing and No. 260 solvent oil is 10;
(4) Roasting the spheroidal micro powder by adopting a special series graphitizing furnace for 12 hours at 2800 ℃, and then naturally cooling;
(5) And grinding the cooled graphite powder by using a vertical mill with a hemispherical ceramic roller surface, and classifying by 5 grades to obtain 5 types of lithium ion battery cathode material products with the particle sizes of D50= (22 +/-2) mu m, D50= (19 +/-2) mu m, D50= (16 +/-2) mu m, D50= (13 +/-2) mu m and D50= (10 +/-2) mu m respectively, wherein the first discharge specific capacitance is not less than 370 (mA · h)/g.
Compared with the example 2, in the step 1, the roasting time of the quasi-spherical micro powder in the step 4 is increased from 8h to 12h, the roasting temperature is increased from 2600 ℃ to 2800 ℃, other conditions are not changed, and the first discharge specific capacitance of the finally obtained negative electrode material is increased from 340 (mA · h)/g to 350 (mA · h)/g, which shows that the roasting temperature and the roasting time are important factors influencing the electricity storage performance of the negative electrode material of the lithium ion battery.
Compared with the example 3, in the step (3), the dosage of the asphalt is increased (the dosage of the solvent oil is increased correspondingly), and the coating reaction is carried out for 4 hours in a reaction kettle at the temperature of 200 ℃; and (5) dividing the obtained cathode material into 5 particle fractions, keeping other conditions unchanged, and increasing the first discharge specific capacitance of the finally obtained cathode material from 340 (mA · h)/g to 350 (mA · h)/g, which shows that the asphalt dosage, the coating temperature and the coating time are important factors influencing the electricity storage performance of the cathode material of the lithium ion battery.
Compared with the example 4, in the step (5), the step (5) is divided into 5 particle fractions, other conditions are not changed, the first discharge specific capacitance of the finally obtained negative electrode material is increased from 360 (mA · h)/g to 370 (mA · h)/g, and the classified particle size is an important factor influencing the electricity storage performance of the negative electrode material of the lithium ion battery.
Comparative example 1
Comparative example 2
In comparison to example 4, step 3 of comparative example 2: the mass ratio of the 5-30 mu m micro powder to the coal tar pitch and the No. 260 solvent oil is 10, 0.9, the coating reaction is carried out for 4 hours in a reaction kettle at 200 ℃ to form a sphere-like shape, other steps and conditions are unchanged, and the first discharge specific capacitance of the prepared lithium battery negative electrode material is only 360 (mA.h)/g. The scale graphite balling tailing is directly related to the first discharge specific capacitance of the lithium battery cathode material.
The application has the advantages that:
1. according to the method, the carbon in the waste cathode of the electrolytic aluminum has a graphene structure, and after high-temperature purification and graphitization, the graphite content of the graphene structure is increased, the graphene structure is more complete, the impurity content is reduced to be below 0.01%, and the energy density is higher than that of an artificial graphite cathode material and a natural graphite cathode material;
2. according to the characteristics of large bulkiness, lubrication, high strength, strong toughness and the like of the waste cathode, fine waste cathode particles are obtained by adopting a process of coarse crushing, magnetic separation, fine crushing of a ceramic roller surface vertical mill and wind power classification by using an impact crusher, so that the grinding efficiency of the waste cathode is improved;
3. the purification and graphitization waste cathode is purified by adopting an Acheson furnace with a flue gas volatilization system or a serial Acheson furnace, and the equipment is mature;
4. the method adopts the conventional anode material coating material and process, and adopts environment-friendly solvent oil as the flux of asphalt;
5. the application adopts a vertical mill and a multi-stage wind power grading process to realize a set of process and various products, and improves the product yield and the production efficiency;
6. the application realizes high-value utilization of the waste cathode (hazardous waste).
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for producing graphite cathode materials of lithium electronic batteries by adopting aluminum electrolysis waste cathodes is characterized by comprising the following steps:
carrying out coarse crushing and first grinding on the aluminum electrolysis waste cathode carbon blocks to obtain micro powder, and mixing the micro powder, asphalt, natural graphite granulation tailings and a solvent for coating to obtain a sphere-like coating material;
roasting and graphitizing the quasi-spherical coating material, and performing secondary grinding and multi-level wind classification on the cooled material to obtain the graphite cathode material of the lithium ion battery with different particle levels.
2. The method according to claim 1, wherein the coarse crushing is carried out by a two-stage impact crusher to obtain particles having a particle size of 50mm or less.
3. The method according to claim 2, wherein during the treatment of the two-stage impact crusher, the feed particle size of the first stage is 500mm or less, and the discharge particle size is 100mm or less;
preferably, the materials of the impact plate and the hammer head of the secondary impact crusher are nodular cast iron with magnetism.
4. The method as claimed in claim 1, wherein the first grinding is performed by a vertical mill and an air classifier, and magnetic separation and iron removal are performed after the first grinding is finished, so that the particle size of the obtained micro powder is 5-50 μm.
5. The method of claim 1, wherein the solvent comprises mineral spirits and/or white oil;
preferably, the mass ratio of the micro powder, the asphalt, the natural graphite pelletizing tailings and the solvent is 10: (0.6-1.5): (1-2): (0.2-0.4), preferably 10;
preferably, the mineral spirits are No. 260.
6. The method according to claim 1, characterized in that the temperature of the coating is 120 ℃ to 250 ℃, preferably 150 ℃, for 2 to 5h;
preferably, the coating is performed using a kneader or a reaction vessel having a heating function.
7. The method according to claim 1, characterized in that the temperature for calcination graphitization is 2400-3000 ℃ for 8-20h; preferably 2800 ℃ for 12h.
8. The process according to claim 1, characterized in that the roasting graphitization is performed using an Acheson furnace or a series graphitization furnace with a flue gas exhaust system.
9. The method of claim 1, wherein the second grinding is performed by using a vertical mill, and the surfaces of grinding discs and grinding rolls of the vertical mill are made of hemispherical silicon carbide wear-resistant materials.
10. Method according to any of claims 1-9, characterized in that the fractionation of the multi-stage air classification is 3-6 stages, preferably 5 stages.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211689291.0A CN115959656A (en) | 2022-12-27 | 2022-12-27 | Method for producing graphite negative electrode material of lithium electronic battery by adopting aluminum electrolysis waste cathode |
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| CN202211689291.0A CN115959656A (en) | 2022-12-27 | 2022-12-27 | Method for producing graphite negative electrode material of lithium electronic battery by adopting aluminum electrolysis waste cathode |
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