CN115646438B - Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite - Google Patents
Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite Download PDFInfo
- Publication number
- CN115646438B CN115646438B CN202210855593.4A CN202210855593A CN115646438B CN 115646438 B CN115646438 B CN 115646438B CN 202210855593 A CN202210855593 A CN 202210855593A CN 115646438 B CN115646438 B CN 115646438B
- Authority
- CN
- China
- Prior art keywords
- graphite
- waste
- negative electrode
- lithium battery
- ball milling
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 93
- 239000010439 graphite Substances 0.000 title claims abstract description 93
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 239000003463 adsorbent Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- 238000001914 filtration Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000007770 graphite material Substances 0.000 abstract description 4
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 36
- 238000001179 sorption measurement Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000001045 blue dye Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000005486 organic electrolyte Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for preparing a dye adsorbent by using graphite of a negative electrode of a waste lithium battery, which comprises the following steps of preprocessing, filtering negative electrode powder of the waste lithium battery after being soaked in clear water for a period of time, collecting filter residues, and collecting residual waste graphite powder after roasting the filter residues; ball milling, namely mechanically ball milling waste graphite powder; and (3) cleaning, namely cleaning and filtering a ball-milled product, and drying the obtained filter residue to obtain the finished product of the functionalized graphite dye adsorbent. The invention adopts a mechanical ball milling method to successfully convert the waste graphite into the graphite material with certain functionality, thereby realizing the recycling of the waste graphite of the negative electrode of the waste lithium battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to a method for preparing a dye adsorbent by using waste lithium battery negative electrode graphite.
Background
In recent years, lithium ion batteries have been widely used in the application markets of daily consumer electronics, electric automobiles, clean energy electrochemical energy storage and the like due to their good electrochemical properties, such as high energy density, relatively stable charge and discharge performance and the like. However, due to the limited life of lithium batteries, the power battery of China accumulated decommissioning amount of about 20 ten thousand tons (about 25 GWh) in 2020, and the accumulated decommissioning amount of 78 ten thousand tons in 2025 is expected. The waste lithium batteries contain noble metal, battery grade graphite, organic electrolyte and other components, so that if a large number of waste lithium batteries cannot be reasonably recycled, complex environmental problems are necessarily caused, and huge resource waste is generated.
At present, the recycling method of the noble metal of the positive electrode of the retired lithium battery is deeply researched in China. As in Chinese patent (Yang Xuebing, et al, patent number: CN 202010268776.7), the aluminum current collector of the waste lithium battery is rapidly separated from the positive electrode active material by utilizing a plasma technology under the low-temperature condition, so that the high-efficiency recovery of the positive electrode active material of the lithium battery is realized; chinese patent (Zhang Guangwen, et al, patent number: CN 202010660636.4) discloses a multi-process efficient synergistic method for recycling the positive electrode of a retired lithium ion battery, which utilizes pyrolysis parameter regulation and hydraulic crushing methods to realize thermal reduction of high-valence transition metal ions in the positive electrode material and leaching of water-soluble lithium salt.
However, the recycling value of the lithium battery negative electrode graphite material is often neglected due to lower market price. It is estimated that the graphite component accounts for about 21% of the total mass of the lithium battery, and the amount of retired waste graphite in 2025 years can reach more than 16 ten thousand tons, and the waste graphite of the lithium battery has the excellent characteristics of high purity, large interlayer spacing, rich oxidation sites and the like, so that the waste graphite has great economic value when being used for high added value upgrading.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
One of the purposes of the invention is to provide a method for preparing a dye adsorbent by using waste lithium battery negative electrode graphite, so that the waste lithium battery negative electrode waste graphite is recycled.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing dye adsorbent by using waste lithium battery negative electrode graphite comprises,
pretreating, namely soaking negative electrode powder of the waste lithium batteries in clear water for a period of time, filtering, collecting filter residues, roasting the filter residues, and collecting residual waste graphite powder;
ball milling, namely mechanically ball milling waste graphite powder;
and (3) cleaning, namely cleaning and filtering a ball-milled product, and drying the obtained filter residue to obtain the finished product of the functionalized graphite dye adsorbent.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the ball milling, the diameter of the ball used for ball milling is 2-10 mm, and the ball-to-material ratio is 10-14: 1.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the ball milling, the ball milling time is 8-32 hours.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the ball milling, the ball milling time is 24 hours.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the pretreatment, the times of soaking and filtering are 3 times, and the soaking time of each time is 3-4 hours.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the pretreatment, roasting is carried out under the atmosphere of nitrogen, and the flow rate of the nitrogen is 100m 3 /h。
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the pretreatment, the roasting temperature is 500 ℃ and the roasting time is 2 hours.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the cleaning, the ball-milled product is placed in 1mol/L hydrochloric acid solution and magnetically stirred for 24 hours for cleaning.
As a preferable scheme of the method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite, the invention comprises the following steps: in the washing, the number of washing and filtering was 2.
It is a further object of the present invention to provide a functionalized graphite dye adsorbent obtainable by a process as described in any one of the preceding claims.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a mechanical ball milling method to successfully convert the waste graphite into the graphite material with certain functionality, thereby realizing the recycling of the waste graphite of the negative electrode of the waste lithium battery. The dry direct ball milling method avoids adding chemical reagents, reduces the cost to a certain extent, and has the potential of treating waste graphite in a large scale because the ball-material ratio adopted by the invention is relatively low.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an XRD pattern of a functionalized graphite dye adsorbent obtained in example 1 of the invention;
FIG. 2 is a Raman diagram of the functionalized graphite dye adsorbent obtained in example 1 of the present invention;
FIG. 3 is a graph of surface pore size and pore volume of the functionalized graphite dye adsorbent obtained in example 1 of the present invention;
FIG. 4 is a graph showing the effect of the functionalized graphite dye adsorbent of example 1 on adsorbing heavy metal lead and cadmium;
FIG. 5 is a graph showing the effect of the functionalized graphite dye adsorbent of example 1 of the present invention on the adsorption of methylene blue dye in water;
FIG. 6 is an XRD pattern of graphite obtained in comparative example 1 of the present invention;
FIG. 7 is a Raman diagram of the graphite obtained in comparative example 1 of the present invention;
FIG. 8 is a graph showing the effect of the functional graphite dye adsorbent of example 2 on the adsorption of methylene blue dye in water
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Soaking the negative electrode powder of the waste lithium battery in clear water, filtering, and repeatedly treating for 3 times, wherein the soaking time is 3 hours each time. The obtained filtrate contains a small amount of electrolyte and binder as well as lithium ions between graphite intercalation layers, and the filter residue is crude waste graphite powder.
(2) Placing the crude waste graphite powder obtained in the step (1) into a roasting furnace, introducing nitrogen atmosphere into the furnace, and setting the flow of the atmosphere to be 100m 3 And/h, preserving the temperature of the system at 500 ℃ for 2 hours, and obtaining the finished waste graphite powder after roasting. In the roasting process, residual organic electrolyte and binder volatilize from the surface of the waste graphite, and the volatilized gas is absorbed by an exhaust gas absorbing device.
(3) Placing the finished waste graphite powder prepared in the step (2) into a ball mill, setting the ball milling frequency to be 20Hz, and respectively performing ball milling for 8h, 16h, 24h and 32h, wherein the diameter of a small ball is 5mm, and the ball-to-material ratio is 12:1, the product obtained by ball milling is a functionalized graphite dye adsorbent.
The X-ray diffraction (XRD) pattern of the functionalized graphite dye adsorbent obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that as the ball milling time is prolonged, the graphite peak of the prepared sample is significantly weakened, which indicates that the crystal structure of the waste graphite is destroyed during the ball milling process and gradually changes into an amorphous form.
The raman diagram of the functionalized graphite dye adsorbent obtained in example 1 is shown in fig. 2, and as can be seen from fig. 2, the ID peak for representing the defect degree of the waste graphite sample is weakened along with the lengthening of the ball milling time, which indicates that the defect number of the sample surface is reduced in the ball milling process, and the IG peak for representing the tensile vibration intensity among sp2 carbon atoms of the waste graphite is strengthened. As the ball milling time was longer, the ID/IG value for representing the defect degree of the sample showed a tendency to decrease first and then increase, and when the ball milling time was 24 hours, the defect value was the lowest, at which time ID/ig=0.12.
The surface pore diameter and pore volume of the functionalized graphite dye adsorbent obtained in example 1 are shown in fig. 3, and as can be seen from fig. 3, the average pore diameter of the waste graphite sample tends to increase and then decrease along with the increase of the ball milling time, and reaches a high value when the ball milling time is 16 hours; the pore volume of the waste graphite sample shows a growing trend along with the lengthening of the ball milling time, but after the ball milling time exceeds 24 hours, the pore volume of the waste graphite sample does not change significantly. Considering comprehensively, the adsorption capacity of the sample pores is maximum at the ball milling time of 24 hours.
Adsorption experiments were performed using the functionalized graphite dye adsorbent obtained in example 1, and selected contaminants included methylene blue dye (MB), lead/cadmium containing solutions, formulated with MB, lead nitrate and cadmium nitrate, respectively. Each contaminant solution was initially at a concentration of 100mmg/L, 25ml of the contaminant solution and 10mg of the functional graphite dye adsorbent material were added to a 40ml capped glass tube, and the mixture was shaken at room temperature (25 ℃) for 12 hours using a shaker at 250pm rotation speed, filtered through a 0.22m filter membrane after the end of adsorption, and the filtrate was collected for subsequent quantitative analysis.
The adsorption effect of the waste graphite and the functional graphite dye adsorbent material prepared by ball milling on heavy metal lead and cadmium is shown in figure 4, and the adsorption capacity of the waste graphite on the lead and the cadmium is respectively 8.68mg/g and 1.13mg/g; the adsorption capacity of the functional graphite dye adsorbent material prepared by ball milling to heavy metal lead and cadmium is obviously improved.
Wherein, for heavy metal lead, the adsorption capacity reaches the maximum value of 15.25mg/g when the ball milling time is 24 hours. For heavy metal cadmium, the adsorption capacity and the ball milling time are in a linear relation, and the maximum value is reached when the ball milling time is 32 hours.
The adsorption effect of the functionalized graphite dye adsorbent on methylene blue dye in water is shown in fig. 5, and as can be seen from fig. 5a, compared with waste graphite, the functionalized graphite dye adsorbent material prepared by ball milling has better adsorption effect, and the effect is increased along with the increase of ball milling time. The adsorption capacity of waste graphite is only 15.56mg/g, the adsorption capacity of ball milling for 8 hours reaches 65.78mg/g, the adsorption capacity is further increased to 230.20g/g after ball milling is continued for 8 hours, and then the increasing trend of the adsorption capacity is slowed down. This trend is similar to the trend of graphite specific surface area change during ball milling, and fig. 5b reflects the relationship between the adsorption capacity and specific surface area of different materials, so that the adsorption amount of methylene blue on the series of materials depends on the specific surface area of the materials to a certain extent.
Comparative example 1
Commercial pure graphite (commercially available from Adamas Beta) was ball milled under the same conditions for 8h, 16h, 24h and 32h, respectively, according to the procedure of step (3) of example 1.
As shown in fig. 6, the X-ray diffraction (XRD) pattern of the graphite obtained in comparative example 1 was obtained for a commercially pure graphite (002) and (004) having significantly higher peak intensities of Yu Feidan, and the peak positions corresponding to the (002) and (004) crystal planes were gradually shifted to a small angle as the ball milling time was prolonged.
As shown in fig. 7, the raman diagram of the graphite obtained in comparative example 1 shows that, unlike the waste graphite, the defect peak of commercially pure graphite gradually increases and the ID/IG value gradually increases as the ball milling time increases, as seen from fig. 7.
Example 2
(1) Soaking the negative electrode powder of the waste lithium battery in clear water, filtering, and repeatedly treating for 3 times, wherein the soaking time is 3 hours each time. The obtained filtrate contains a small amount of electrolyte and binder as well as lithium ions between graphite intercalation layers, and the filter residue is crude waste graphite powder.
(2) Placing the crude waste graphite powder obtained in the step (1) into a roasting furnace, introducing nitrogen atmosphere into the furnace, and setting the flow of the atmosphere to be 100m 3 And/h, preserving the temperature of the system at 500 ℃ for 2 hours, and obtaining the finished waste graphite powder after roasting. In the roasting process, residual organic electrolyte and binder volatilize from the surface of the waste graphite, and the volatilized gas is absorbed by an exhaust gas absorbing device.
(3) Placing the finished waste graphite powder prepared in the step (2) into a ball mill, setting the ball milling frequency to be 20Hz, the ball milling time to be 24 hours, and the ball diameters to be 5mm and the ball-to-material ratios to be 8 respectively: 1. 10: 1. 12: 1. 14:1, the product obtained by ball milling is a functionalized graphite dye adsorbent.
The adsorption effect of the functional graphite dye adsorbent obtained in example 2 on methylene blue dye in water is shown in fig. 8, and it can be seen that in the experimental test range, as the ball material ratio increases, the adsorption capacity of the waste graphite sample gradually increases, but the ball material ratio exceeds 12: after 1, the adsorption capacity of the waste graphite sample was not significantly increased.
Example 3
(1) Soaking the negative electrode powder of the waste lithium battery in clear water, filtering, and repeatedly treating for 3 times, wherein the soaking time is 3 hours each time. The obtained filtrate contains a small amount of electrolyte and binder as well as lithium ions between graphite intercalation layers, and the filter residue is crude waste graphite powder.
(2) Placing the crude waste graphite powder obtained in the step (1) into a roasting furnace, introducing nitrogen atmosphere into the furnace, and setting the flow of the atmosphere to be 100m 3 And/h, preserving the temperature of the system at 500 ℃ for 2 hours, and obtaining the finished waste graphite powder after roasting. In the roasting process, residual organic electrolyte and binder volatilize from the surface of the waste graphite, and the volatilized gas is absorbed by an exhaust gas absorbing device.
(3) Placing the finished waste graphite powder prepared in the step (2) into a ball mill, setting the ball milling frequency to be 20Hz, respectively performing ball milling for 24 hours, wherein the diameter of a small ball is 5mm, and the ball-to-material ratio is 12:1, the ball-milled product is a functionalized graphite dye adsorbent and is marked as MG24.
(4) Putting the product of the step (3) into a 1mol/L hydrochloric acid solution, magnetically stirring for 24 hours, and repeatedly flushing a solid sample by using deionized water until the leaching solution is neutral; and filtering and collecting solid powder, putting the obtained filter cake into a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the prepared functionalized graphite dye adsorbent material.
The materials synthesized under different potassium permanganate concentrations are analyzed by adopting a Raman spectrum method, and the materials are introducedExperimental group containing potassium permanganate, 1580cm -1 The graphitized G peak is obviously weakened relative to MG24-0, 1350cm -1 D peak representing defect at 2700cm -1 The 2D peak was accompanied by a decrease at night, and the extent of decrease increased with increasing concentration, until after 20mmol, the D peak, the 2D peak, had almost disappeared, and the G peak remained only as a small peak. In addition, when potassium permanganate is introduced into the system, the wave number is 600-700 cm -1 Between which MnO is present 2 Is a characteristic peak of (2).
Example 4
(1) Soaking the negative electrode powder of the waste lithium battery in clear water, filtering, and repeatedly treating for 3 times, wherein the soaking time is 3 hours each time. The obtained filtrate contains a small amount of electrolyte and binder as well as lithium ions between graphite intercalation layers, and the filter residue is crude waste graphite powder.
(2) Placing the crude waste graphite powder obtained in the step (1) into a roasting furnace, introducing nitrogen atmosphere into the furnace, and setting the flow of the atmosphere to be 100m 3 And/h, preserving the temperature of the system at 500 ℃ for 2 hours, and obtaining the finished waste graphite powder after roasting. In the roasting process, residual organic electrolyte and binder volatilize from the surface of the waste graphite, and the volatilized gas is absorbed by an exhaust gas absorbing device.
(3) Placing the finished waste graphite powder prepared in the step (2) into a ball mill, setting the ball milling frequency to be 20Hz, respectively performing ball milling for 24 hours, wherein the diameter of a small ball is 5mm, and the ball-to-material ratio is 12:1, the ball-milled product is a functionalized graphite dye adsorbent and is marked as MG24.
(4) Putting the product of the step (3) into a 1mol/L hydrochloric acid solution, magnetically stirring for 24 hours, and repeatedly flushing a solid sample by using deionized water until the leaching solution is neutral; and filtering and collecting solid powder, putting the obtained filter cake into a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the prepared functionalized graphite dye adsorbent material.
The mechanical ball milling method provided by the invention successfully converts waste graphite into graphite materials with certain functionality. The dry direct ball milling method avoids adding chemical reagents, crushing and stripping graphite under the action of mechanical force to generate thin-layer graphite or graphene, avoids introducing strong acid and strong oxidizing reagents in the traditional method such as Hummers method, reduces the cost to a certain extent, and in addition, the ball-material ratio adopted by the method is relatively low, so that the method can be considered to have the potential of treating waste graphite in a large scale, and the mechanical ball milling method is widely applied in a plurality of industries from the practical application point of view, so that the method can be an effective solution to the problems of low-cost treatment and reuse of a large amount of waste graphite.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A method for preparing dye adsorbent by using waste lithium battery negative electrode graphite is characterized in that: the steps are as follows,
pretreating, namely soaking negative electrode powder of the waste lithium batteries in clear water for a period of time, filtering, collecting filter residues, roasting the filter residues, and collecting residual waste graphite powder;
ball milling, namely mechanically ball milling waste graphite powder; in the ball milling, the diameter of a ball used for ball milling is 2-10 mm, and the ball-to-material ratio is 10-14: 1, a step of; in the ball milling, the ball milling time is 8-32 hours;
and (3) cleaning, namely cleaning and filtering a ball-milled product, and drying the obtained filter residue to obtain the functional graphite dye adsorbent.
2. The method for preparing dye adsorbent by using waste lithium battery negative electrode graphite as claimed in claim 1, wherein: in the pretreatment, the times of soaking and filtering are 3 times, and the soaking time of each time is 3-4 hours.
3. The method for preparing dye adsorbent by using waste lithium battery negative electrode graphite as claimed in claim 2, wherein: in the pretreatment, roasting is carried out under nitrogen atmosphere,the nitrogen flow is 100m 3 /h。
4. A method for preparing dye adsorbent by waste lithium battery negative electrode graphite as claimed in claim 3, characterized in that: in the pretreatment, the roasting temperature is 500 ℃ and the roasting time is 2 hours.
5. The method for preparing the dye adsorbent by using the waste lithium battery negative electrode graphite according to any one of claims 1 to 4, which is characterized in that: in the cleaning, the ball-milled product is placed in 1mol/L hydrochloric acid solution and magnetically stirred for 24 hours for cleaning.
6. The method for preparing dye adsorbent by using waste lithium battery negative electrode graphite as claimed in claim 5, wherein: in the washing, the number of washing and filtering was 2.
7. A functional graphite dye adsorbent obtainable by the method of any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855593.4A CN115646438B (en) | 2022-07-20 | 2022-07-20 | Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855593.4A CN115646438B (en) | 2022-07-20 | 2022-07-20 | Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115646438A CN115646438A (en) | 2023-01-31 |
| CN115646438B true CN115646438B (en) | 2024-04-02 |
Family
ID=85023447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210855593.4A Active CN115646438B (en) | 2022-07-20 | 2022-07-20 | Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115646438B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101621312B1 (en) * | 2015-10-15 | 2016-05-16 | 이치헌 | Method Of Recycling Resource for lithium ion secondary battery |
| CN109745948A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | One kind except cadmium adsorbent, and its preparation method and application |
| CN112591737A (en) * | 2020-12-16 | 2021-04-02 | 昆明理工大学 | Method for preparing carbon nanohorn by recycling waste lithium ion battery cathode graphite |
| CN113437378A (en) * | 2021-06-17 | 2021-09-24 | 华南理工大学 | Method for recycling and reusing anode and cathode of waste battery |
| WO2021223597A1 (en) * | 2020-05-07 | 2021-11-11 | 广东邦普循环科技有限公司 | Oxygen reduction catalyst employing graphite of negative electrode of waste battery, and preparation method therefor |
-
2022
- 2022-07-20 CN CN202210855593.4A patent/CN115646438B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101621312B1 (en) * | 2015-10-15 | 2016-05-16 | 이치헌 | Method Of Recycling Resource for lithium ion secondary battery |
| CN109745948A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | One kind except cadmium adsorbent, and its preparation method and application |
| WO2021223597A1 (en) * | 2020-05-07 | 2021-11-11 | 广东邦普循环科技有限公司 | Oxygen reduction catalyst employing graphite of negative electrode of waste battery, and preparation method therefor |
| CN112591737A (en) * | 2020-12-16 | 2021-04-02 | 昆明理工大学 | Method for preparing carbon nanohorn by recycling waste lithium ion battery cathode graphite |
| CN113437378A (en) * | 2021-06-17 | 2021-09-24 | 华南理工大学 | Method for recycling and reusing anode and cathode of waste battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115646438A (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112047335B (en) | Combined treatment method for black powder of waste lithium ion battery | |
| CN111285366A (en) | Regeneration method of lithium ion battery negative electrode graphite | |
| CN115207320A (en) | Preparation method of lithium/sodium ion battery negative electrode material | |
| CN114180568B (en) | Pretreated microcrystalline graphite, negative electrode active material, and preparation and application thereof | |
| EP4151593A1 (en) | Method for graphite purification and lattice reconstruction in power battery | |
| CN114614133B (en) | Combined treatment method for betel nut residues and waste anode materials | |
| CN114335781A (en) | Method for extracting precious metal from waste lithium battery | |
| CN114835104B (en) | Hard carbon material, preparation method and application thereof, and sodium ion battery | |
| CN108550841A (en) | A kind of preparation method of hard carbon cathode material, preparation method, lithium ion battery and the battery | |
| CN113415814B (en) | Method for selectively recovering lithium from waste lithium ion batteries by using ultralow-temperature roasting | |
| CN114212786A (en) | Method for preparing high-capacity high-rate graphite by taking waste lithium ion battery cathode material as raw material | |
| CN115646438B (en) | Method for preparing dye adsorbent by using waste lithium battery negative electrode graphite | |
| CN110563046B (en) | Method for recycling waste lithium ion battery anode material | |
| CN110061227B (en) | Lithium battery cathode material with nano silicon remaining in carbon shell and manufacturing method and application thereof | |
| CN115662804A (en) | Method for preparing supercapacitor electrode material by using waste lithium battery graphite | |
| JP2006024747A (en) | Carbon material for electric double-layer capacitor electrode, and its production method | |
| GB2616099A (en) | Precise fluorination and purification method for ginkgo leaf, and functional use of primary lithium battery | |
| CN115285969A (en) | Biomass-derived nitrogen-doped hard carbon material and preparation method and application thereof | |
| CN116177520A (en) | High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof | |
| CN114188522A (en) | Microcrystalline graphite/CNT @ C composite material, preparation method thereof and application thereof in lithium secondary battery | |
| CN114408916A (en) | Expanded graphite and preparation method thereof | |
| CN111468502B (en) | Heavy metal polluted plant stem treatment and high-value utilization method | |
| CN116404293B (en) | Waste lithium battery graphite negative electrode recycling method based on oil sludge microwave pyrolysis cladding | |
| Dong et al. | Spent graphite regeneration: Exploring diverse repairing manners with impurities-catalyzing effect towards high performance and low energy consumption | |
| CN114950361B (en) | Method for preparing composite adsorbent through waste lithium batteries |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |