CN114634181B - Lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge and preparation method thereof - Google Patents
Lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge and a preparation method thereof. Drying, grinding and sieving the electroplating sludge, adding an inorganic acid solution, stirring uniformly, performing acid leaching reaction, and centrifuging to obtain an electroplating sludge leaching solution; centrifuging the chlorella concentrate to obtain active chlorella cells; adding the obtained active chlorella cells into a mixed solution of electroplating sludge leaching solution and water, stirring and mixing, washing and drying to obtain a composite material precursor, grinding and mixing with a certain proportion of potassium series activating agent, calcining at high temperature in an inert or reducing atmosphere, and washing potassium salt from carbonized products by water to obtain the productFe 3 C@NPC lithium sulfur battery cathode material. The preparation method not only solves the environmental problem of electroplating sludge, but also prepares the high-valued lithium sulfur battery positive electrode material by utilizing the biological adsorption capacity and unique morphology of the bioactive chlorella cells, thereby providing a feasible thought for changing the environmental waste into valuables.
Description
Technical Field
The invention belongs to the technical field of electroplating sludge treatment, and particularly relates to a lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge and a preparation method thereof.
Background
The electroplating sludge is a dangerous solid waste, contains a large amount of toxic and harmful heavy metals such as copper, nickel, chromium, zinc, iron, cadmium and the like, has the characteristics of instability, strong migration and high water content, and if the electroplating sludge is not properly treated and stacked at will, the heavy metals in the electroplating sludge can migrate along the path of sludge, soil, crops and human bodies under the action of rain water leaching, so that the electroplating sludge not only pollutes the environment, but also causes harm to the health of the human bodies. Moreover, different electroplating enterprises or electroplating processes generate different electroplating sludge, so that different treatment methods are required. In general, electroplating sludge can be divided into two categories: the sludge is classified, the heavy metal elements contained in the sludge are single, the treatment is relatively simple, and the sludge is easier to recycle; the other type is mixed sludge, which contains complex heavy metal elements, often contains dangerous heavy metals such as chromium, cadmium and the like, and has huge treatment and disposal difficulty and is not easy to separate and recycle. The mixed sludge generally contains a large amount of iron elements, and is mixed with other heavy metals, so that the difficulty of separating and recycling the sludge is increased. The current common electroplating sludge treatment technology mainly comprises the following steps: stabilization/solidification technology, heat treatment technology, bioleaching, smelting technology and roasting leaching technology, materialization technology, etc., and the above treatment technology has the disadvantages of excessively high cost, secondary pollution risk, etc., so that it is necessary to develop a new technical method for treating electroplating sludge.
Yellow et al developed a Fe by using a simple single-pot electrostatic spinning method 3 C/Carbon Nanofiber (CNF) suspended film as separator for lithium sulfur battery, the separator providingThe large number of macropores within the nanofiber web are (i) to facilitate ion transport and electrolyte permeation, (ii) nitrogen-containing functional groups to trap soluble polysulfides by strong interatomic attraction, and (iii) electron/ion transfer is greatly enhanced due to the high conductivity of the CNF web. However, fe 3 The specific surface area of the C/Carbon Nanofiber (CNF) is only 62m 2 Per g, fe cannot be fully exerted 3 C anchoring and catalytic decomposition of lithium polysulfide, therefore, fe 3 The specific capacity of the lithium sulfur battery with the C/Carbon Nanofiber (CNF) suspended film as a diaphragm is attenuated by 24% after 100 times of circulation, the average attenuation of each circle is 0.24%, and the circulation stability is far insufficient to meet the commercialization requirement of the lithium sulfur battery, so that the Fe with high specific surface area needs to be developed 3 C/carbon nanomaterial to improve Long cycling performance of lithium sulfur batteries (Huang, jian-Qia; zhang, biao; xu, zheng-Long; abouali, sara; akbari Garakani, mohammad; huang, jiaqiang; kim, jang-Kyo. Novel interlayer made from Fe) 3 C/carbon nanofiber webs for high performance lithium-sulfur batteries.Journal of Power Sources,285(2015),43-50)。
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge and a preparation method thereof, in particular to a method for preparing the lithium-sulfur battery positive electrode material by recycling iron in mixed electroplating sludge and wrapping other heavy metals in the material so as to realize innocuity. The method of the invention utilizes the iron in the electroplating sludge to a high value, thus not only providing a new idea for innocuous treatment of the mixed electroplating sludge, but also providing a new method for preparing the electrochemical energy storage material.
The preparation method comprises the steps of drying, grinding and sieving electroplating sludge, adding an inorganic acid solution, uniformly stirring, performing acid leaching reaction, and centrifuging to obtain electroplating sludge leaching liquid; centrifuging the chlorella concentrate to obtain active chlorella cells; adding the obtained active chlorella cells into electroplating sludge leaching solution, stirring and mixing, washing and drying to obtain a composite material precursor, grinding and mixing with a certain proportion of potassium activator, and finally carrying out inert or still-adding treatmentCalcining at high temperature in original atmosphere, washing potassium salt from carbonized product with water to obtain Fe 3 C@NPC lithium sulfur battery cathode material. The preparation method not only solves the environmental problem of electroplating sludge, but also prepares the high-valued lithium sulfur battery positive electrode material by utilizing the biological adsorption capacity and unique morphology of the bioactive chlorella cells, thereby providing a feasible thought for changing the environmental waste into valuables.
The invention aims at realizing the following technical scheme:
the invention provides a method for preparing a lithium-sulfur battery positive electrode material by recycling iron in electroplating sludge, which comprises the following preparation steps:
(1) Drying, grinding and sieving the electroplating sludge, adding an inorganic acid solution, uniformly stirring and mixing for a period of time, and centrifugally filtering to obtain an electroplating sludge leaching solution;
(2) Centrifugally separating and washing the concentrated chlorella liquid to obtain active chlorella cells;
(3) Adding the active chlorella cells obtained in the step (2) into the mixed solution of the electroplating sludge leaching solution and water obtained in the step (1), stirring and mixing, and then washing and drying to obtain a composite material precursor;
(4) Calcining the composite material precursor mixed alkaline activator obtained in the step (3) at high temperature in inert or reducing atmosphere to obtain Fe 3 A mixture of C@NPC and an alkaline activator;
(5) Fe obtained in the step (4) 3 Soaking the mixture of C@NPC and an alkaline activator in water or acid, filtering, washing and drying to obtain Fe 3 C@NPC lithium sulfur battery cathode material.
Further, the step (1) of drying, grinding and sieving refers to drying at 60-120 ℃ for 6-48 hours, and grinding and sieving by a sieve with 50-500 meshes.
Further, the inorganic acid solution in the step (1) is hydrochloric acid, sulfuric acid solution or nitric acid solution; the concentration of the inorganic acid solution in the step (1) is 1-10 mol/L.
Further, the concentration of the inorganic acid solution in the step (1) is 1-5 mol/L.
Further, the stirring speed in the step (1) is 50-500 rpm, and the stirring time in the step (1) is 2-24 h.
Further, the rotational speed of the centrifugal concentration chlorella liquid in the step (2) is 5000-10000 revolutions per minute, and the time is 1-5 minutes.
Further, the ratio of the mass of the activated chlorella cells added in the step (3) to the volume of the electroplating sludge leaching solution is 1-50 g/L.
Further, the stirring and mixing speed in the step (3) is 50-500 rpm.
Further, the stirring and mixing time in the step (3) is 1-24 h.
Further, in the step (3), stirring and mixing are carried out for 6-24 hours.
Further, the solvent for washing in the step (3) is one or a mixed solution of water and ethanol.
Further, the drying in the step (3) is at least one of normal pressure drying, vacuum drying and freeze drying.
Further, the alkaline activator is a potassium activator.
Further, in the step (4), the alkaline activator is one or more of potassium hydroxide, potassium carbonate, potassium chloride and potassium bicarbonate.
Further, the addition amount of the alkaline activator in the step (4) is 0.5 to 5 times of the mass of the precursor of the composite material obtained in the step (3).
Further, the addition amount of the alkaline activator in the step (4) is 0.5 to 4 times of the mass of the precursor of the composite material obtained in the step (3).
Further, in the step (4), the inert or reducing atmosphere is one or more of nitrogen and argon.
Further, the mixing method of the alkaline activator in the step (4) and the composite material precursor obtained in the step (3) is grinding and stirring, and the time is 5-30 minutes.
Further, the high-temperature calcination in the step (4) means calcination in which the temperature is raised to 800-900 ℃ for 1-10 hours at a heating rate of 1-10 ℃/min.
Further, the high-temperature calcination time in the step (4) is 1 to 6 hours.
Further, the washing in the step (5) is performed by using distilled water, hydrochloric acid or a mixed solution of distilled water and hydrochloric acid.
Further, the drying in the step (5) is at least one of normal pressure drying, vacuum drying and freeze drying.
The invention also provides Fe prepared by the preparation method 3 C@NPC lithium sulfur battery cathode material.
Compared with the prior art, the invention has the following advantages:
(1) The active chlorella cells adopted by the invention are used as algae microorganisms, and have the advantages of wide distribution, rapid growth, simple harvesting, low cost, green and harmless property, and biological activity, and can adsorb and mineralize heavy metal ions; the biological macromolecules such as proteins, phospholipids and the like in the chlorella can dope heteroatoms such as nitrogen, phosphorus and the like into the carbon material framework in the carbonization process, so that the conductivity of the carbon material is improved, the activity defect is increased, and the kinetics of the reaction is enhanced.
(2) The invention utilizes layered porous Fe after carbonization of active chlorella cells adsorbed with heavy metals 3 On one hand, the layered porous NPC (nuclear pore compound) matrix not only effectively adapts to the volume change of sulfur, but also reduces the transmission distance of lithium ions and increases the reaction contact area of the lithium-sulfur battery sulfur simple substance carrier; on the other hand, fe 3 The synergistic effect of the C nano particles and N, P hetero atoms effectively improves the conductivity of the electrode and the adsorption capacity of the electrode to soluble LiPS, and promotes Li 2 Decomposition of S. Fe obtained 3 The C@NPC lithium sulfur battery positive electrode material has excellent cycling stability and higher capacity, and can meet the requirements of the current market.
(3) Fe prepared by the invention 3 The active chlorella cells in the positive electrode material of the C@NPC lithium sulfur battery are partially graphitized after being calcined at a high temperature, so that transfer and diffusion of Li ions are facilitated.
(4) The invention recovers and utilizes the dangerous solid waste electroplating sludge with high value, and can solve the problem of environmental pollution.
(5) The preparation method has the advantages of simple process, simple and convenient operation and convenient control.
Drawings
FIG. 1 is Fe prepared in example 1 3 XRD pattern of positive electrode material of C@NPC lithium sulfur battery.
FIG. 2 is Fe prepared in example 1 3 SEM image of c@npc lithium sulfur battery cathode material.
FIG. 3 is Fe prepared in example 2 3 The positive electrode material of the C@NPC lithium sulfur battery is assembled into a cycle performance diagram of the button lithium sulfur battery when the current density is 1C.
FIG. 4 is Fe prepared in example 2 3 Raman spectrum diagram of positive electrode material of C@NPC lithium sulfur battery.
FIG. 5 is Fe prepared in example 3 3 The positive electrode material of the C@NPC lithium sulfur battery is assembled into a cycle performance diagram of the button lithium sulfur battery when the current density is 0.5 ℃.
FIG. 6 is Fe prepared in example 3 3 The positive electrode materials of the C@NPC lithium sulfur battery are assembled into a multiplying power performance diagram of the button battery under different current densities.
FIG. 7 is Fe prepared in example 1 3 Nitrogen adsorption/desorption curve graph of positive electrode material of C@NPC lithium sulfur battery.
Detailed Description
Specific implementations of the invention are further described below with reference to the drawings and examples, but the implementation and protection of the invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
(1) Electroplating sludge leaching solution: the electroplating sludge is placed in a blast drying oven, dried for 48 hours at 60 ℃, ground and sieved by a 50-mesh sieve. Taking 20g of dried electroplating sludge, adding 100mL of hydrochloric acid with the concentration of 1mol/L, wherein the 100mL of hydrochloric acid with the concentration of 1mol/L is obtained by adding 10mL of concentrated hydrochloric acid (10 mol/L) into distilled water to fix the volume to 100mL, adding a rotor, stirring for 24h at 50 rpm, and centrifuging for 1 min at 10000 rpm to obtain supernatant serving as an electroplating sludge leaching solution;
(2) Active chlorella cell isolation: adding 100mL of concentrated chlorella liquid into two centrifuge tubes, centrifuging for 1 min at 10000 revolutions per minute, and then rinsing with distilled water for three times to obtain active chlorella cells;
(3) Adding 0.1g of active chlorella cells into a mixed solution of 50mL of electroplating sludge leaching solution and 50mL of distilled water, adding a rotor, and stirring for 24 hours at 50 rpm to obtain a composite material precursor;
(4) Washing the composite material precursor with distilled water for three times, and freeze-drying to obtain a dried composite material precursor;
(5) Mixing the dried composite material precursor with potassium bicarbonate according to a mass ratio of 2:1, mixing, grinding for 5 minutes to obtain a mixture of a grinded dry composite material precursor and potassium bicarbonate;
(6) Heating the mixture of the ground dry composite material precursor and potassium bicarbonate to 800 ℃ at a heating rate of 1 ℃/min under nitrogen atmosphere, calcining for 6 hours, cooling, soaking in distilled water for 3 hours, and then filtering and drying to obtain Fe 3 C@NPC lithium sulfur battery cathode material.
Fe prepared in this example 3 The physicochemical property characterization of the C@NPC lithium sulfur battery positive electrode material is shown in fig. 1 and 2, and fig. 1 is prepared Fe 3 As can be seen from FIG. 1, XRD (X-ray diffraction) patterns of the positive electrode material of the C@NPC lithium-sulfur battery show Fe prepared in example 1 3 C@NPCFe 3 Iron carbide exists in the positive electrode material of the C@NPC lithium sulfur battery. FIG. 2 is a prepared Fe 3 SEM (scanning electron microscope) image of the positive electrode material of the c@npc lithium sulfur battery. As can be seen from FIG. 1, SEM shows Fe prepared in example 1 3 The C@NPC lithium sulfur battery positive electrode material has good appearance, and chlorella is carbonized into a layered porous spherical carbon material. FIG. 7 is Fe prepared in example 1 3 C@NPC lithium sulfur battery positive electrode material nitrogen adsorption/desorption curve graph, and according to BET calculation result analysis, fe 3 The pores of the positive electrode material of the C@NPC lithium sulfur battery are mainly micropores, and the specific surface area is up to 1777m 2 And/g. The high micropore specific surface area is beneficial to increasing the contact area of the electrolyte and the electrode material, andthe transmission distance of lithium ions is shortened, and the reaction rate can be effectively improved.
Example 2
(1) Electroplating sludge leaching solution: the electroplating sludge is placed in a blast drying oven, dried for 6 hours at 120 ℃, ground and sieved by a 500-mesh sieve. Taking 20g of dried electroplating sludge, adding 20mL of concentrated sulfuric acid (10 mol/L), adding a rotor, stirring for 2 hours at 500 rpm, and centrifuging for 5 minutes at 5000 rpm to obtain supernatant serving as electroplating sludge leaching liquid;
(2) Active chlorella cell isolation: adding 100mL of concentrated chlorella liquid into two centrifuge tubes, centrifuging for 5 minutes at 5000 rpm, and then rinsing with distilled water for three times to obtain active chlorella cells;
(3) Adding 1g of active chlorella cells into a mixed solution of 20mL of electroplating sludge leaching solution and 80mL of distilled water, adding a rotor, and stirring for 1h at 500 rpm to obtain a composite material precursor;
(4) Washing the composite material precursor with absolute ethyl alcohol for three times, and then drying in vacuum to obtain a dried composite material precursor;
(5) Mixing the dried composite material precursor with potassium hydroxide according to a mass ratio of 1:4, and grinding for 30 minutes to obtain a mixture of the ground dried composite material precursor and potassium hydroxide;
(6) Calcining the mixture of the ground dry composite material precursor and potassium hydroxide at the temperature rising rate of 10 ℃/min to 900 ℃ for 1h under the argon atmosphere, cooling, soaking in distilled water for 3 h, and then filtering and drying to obtain Fe 3 C@NPC lithium sulfur battery cathode material.
Example 2 Fe obtained 3 The positive electrode material of the C@NPC lithium sulfur battery is assembled into a button lithium sulfur battery, and the discharge capacity of the button lithium sulfur battery is tested, and the button lithium sulfur battery is charged and discharged within the range of 1.7-2.8V. The current density 1C long cycle stability test is shown in fig. 3. Meanwhile, fe 3 The positive electrode material of the C@NPC lithium sulfur battery can be stably circulated to more than 500 circles, and the average attenuation of each circle is 0.06%. Fe prepared in example 2 3 The physicochemical property characterization of the positive electrode material of the C@NPC lithium sulfur battery is shown in FIG. 4, and FIG. 4 is Fe prepared in example 2 3 Positive C@NPC lithium sulfur batteryRaman data of polar material and graphitic carbon, fe in fig. 4 3 I of C@NPC lithium sulfur battery positive electrode material D /I G Larger than graphite carbon, indicating that Fe 3 Chlorella cells in the C@NPC lithium sulfur battery positive electrode material anneal N, P and other heteroatoms and Fe at high temperature 3 C is doped into the carbon layer, more active sites and defects are added, which not only helps to improve the conductivity and the adsorption capacity of the electrode to soluble LiPS, but also can promote Li 2 S is decomposed, so that the electrochemical performance of the material is improved.
Example 3
(1) Electroplating sludge leaching solution: the electroplating sludge is placed in a blast drying oven, dried for 12 hours at 80 ℃, ground and sieved by a hundred-mesh sieve. Taking 20g of dried electroplating sludge, adding 20mL of nitric acid solution with the concentration of 5mol/L, wherein the 20mL of nitric acid solution with the concentration of 5mol/L is obtained by adding 10mL of concentrated nitric acid (10 mol/L) into distilled water to fix the volume to 20mL, adding a rotor, stirring for 6h at 200 rpm, and centrifuging for 3 min at 8000 rpm to obtain supernatant serving as an electroplating sludge leaching solution;
(2) Active chlorella cell isolation: adding 100mL of concentrated chlorella liquid into two centrifuge tubes, centrifuging for 3 minutes at 8000 revolutions per minute, and then rinsing with distilled water for three times to obtain active chlorella cells;
(3) Adding 0.2g of active chlorella cells into a mixed solution of 10mL of electroplating sludge leaching solution and 90mL of distilled water, adding a rotor, and stirring for 12h at 200 rpm to obtain a composite material precursor;
(4) Washing the composite material precursor with 0.6g/mL alcohol for three times, and drying by blowing to obtain a dried composite material precursor;
(5) Mixing the dried composite material precursor with potassium carbonate according to a mass ratio of 1:2, and grinding for 10 minutes to obtain a mixture of the ground dried composite material precursor and the potassium carbonate;
(6) Calcining the mixture of the ground dry composite material precursor and potassium carbonate for 2 hours at the temperature rising rate of 3 ℃/min to 850 ℃ in nitrogen atmosphere, cooling, soaking in distilled water for 3 hours, and then filtering and drying to obtain Fe 3 C@NPC lithium sulfurA battery positive electrode material.
Fe obtained in example 3 3 The positive electrode material of the C@NPC lithium sulfur battery is assembled into a button lithium sulfur battery, the charge and discharge capacity of the button lithium sulfur battery are tested, and the cycle life test is carried out within the range of 1.7-2.8V. FIG. 5 is a diagram of Fe prepared in example 3 3 C@NPC lithium sulfur battery cathode material cyclic stability test chart (current density is 0.5C). As can be seen from FIG. 5, after 350 charge-discharge cycles, fe 3 The lithium sulfur battery with the C@NPC as the positive electrode material of the lithium sulfur battery can also provide 600mAhg -1 Is a high reversible specific capacity of (a), and an average attenuation of 0.093% per turn. As shown in FIG. 6, the rate performance of the fabricated button cell at different current densities is shown, and as can be seen from FIG. 6, fe 3 The C@NPC lithium sulfur battery positive electrode material has excellent rate capability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the lithium sulfur battery positive electrode material prepared by recycling iron in electroplating sludge is characterized by comprising the following preparation steps:
(1) Drying, grinding and sieving the electroplating sludge, adding an inorganic acid solution, uniformly stirring, reacting with the acid, and centrifuging to obtain an electroplating sludge leaching solution;
(2) Centrifugally separating and washing the concentrated chlorella liquid to obtain active chlorella cells;
(3) Adding the active chlorella cells obtained in the step (2) into the mixed solution of the electroplating sludge leaching solution and water obtained in the step (1), stirring and mixing, and then washing and drying to obtain a composite material precursor;
(4) Mixing the composite material precursor obtained in the step (3) with a potassium activator, and calcining in an inert or reducing atmosphere to obtain Fe 3 A mixture of C@NPC and a potassium activator;
(5) Fe obtained in the step (4) 3 Mixing of C@NPC and potassium saltLeaching the compound with water or acid, filtering, and drying to obtain Fe 3 C@NPC lithium sulfur battery cathode material.
2. The method for preparing the lithium-sulfur battery positive electrode material prepared by recycling iron in electroplating sludge according to claim 1, wherein the drying, grinding and sieving in the step (1) means that the drying, grinding and sieving are carried out for 6-48 hours at 60-120 ℃ and the grinding and sieving are carried out through a 50-500-mesh sieve.
3. The method for preparing a positive electrode material of a lithium-sulfur battery by recovering iron from electroplating sludge according to claim 1, wherein the inorganic acid solution in the step (1) is hydrochloric acid, nitric acid solution or sulfuric acid solution; the concentration of the inorganic acid solution in the step (1) is 1-10 mol/L.
4. The method for preparing the lithium sulfur battery positive electrode material prepared by recycling iron in electroplating sludge according to claim 1, wherein the stirring speed in the step (1) is 50-500 rpm, and the stirring time in the step (1) is 2-24 h.
5. The method for preparing a lithium sulfur battery positive electrode material prepared by recovering iron from electroplating sludge according to claim 1, wherein the ratio of the mass of the activated chlorella cells added in the step (3) to the volume of the electroplating sludge leaching solution is 1-50 g/L.
6. The method for preparing a positive electrode material of a lithium-sulfur battery by recycling iron in electroplating sludge according to claim 1, wherein the stirring and mixing time in the step (3) is 1-24 h.
7. The method for preparing a positive electrode material of a lithium-sulfur battery by recycling iron in electroplating sludge according to claim 1, wherein the washing solvent in the step (3) is one or more of water and ethanol.
8. The method for producing a positive electrode material for a lithium-sulfur battery, which is produced by recovering iron from electroplating sludge according to claim 1, wherein the drying in the step (3) is at least one of normal pressure drying, vacuum drying, and freeze drying.
9. The method for producing a positive electrode material for lithium-sulfur batteries, which is produced by recovering iron from electroplating sludge according to claim 1, wherein the potassium-based activator in step (4) is at least one of potassium hydroxide, potassium chloride, potassium carbonate, and potassium bicarbonate; the adding amount of the potassium activator in the step (4) is 0.5 to 5 times of the mass of the precursor of the composite material; the inert or reducing atmosphere in the step (4) is more than one of nitrogen and argon; the calcination in the step (4) is calcination for 1-6 hours at the temperature rising rate of 1-10 ℃/min to 800-900 ℃.
10. The Fe prepared by the preparation method of any one of claims 1 to 9 3 C@NPC lithium sulfur battery cathode material.
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