CN110203963B - Method for recycling overdue zinc gluconate - Google Patents

Method for recycling overdue zinc gluconate Download PDF

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CN110203963B
CN110203963B CN201910359712.5A CN201910359712A CN110203963B CN 110203963 B CN110203963 B CN 110203963B CN 201910359712 A CN201910359712 A CN 201910359712A CN 110203963 B CN110203963 B CN 110203963B
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zinc gluconate
overdue
zno
recycling
zinc
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CN110203963A (en
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侯宏英
王雷
刘显茜
姚远
朱境
邱进旭
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Kunming University of Science and Technology
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract

The invention discloses a method for recycling overdue zinc gluconate, which comprises the steps of adding water into overdue zinc gluconate to prepare a zinc gluconate solution, carrying out pyrolysis carbonization on a product obtained after hydrothermal reaction in nitrogen, cooling to room temperature, cleaning and drying to obtain a ZnO/C composite material; testing the electrochemical lithium storage performance by adopting a constant current charge/discharge method, and investigating the feasibility of the ZnO/C composite material as the lithium ion battery cathode active material; the invention has simple process and environmental protection, and fully exerts the secondary non-medical value in the overdue zinc gluconate.

Description

Method for recycling overdue zinc gluconate
Technical Field
The invention relates to a method for recycling overdue zinc gluconate, and belongs to the technical field of new energy materials.
Background
Zinc is involved in the synthesis process of more than 200 enzymes in human body, has the functions of reducing toxin absorption, stimulating appetite, promoting cell growth and the like, and is an indispensable trace element in human body. Zinc is mainly found in marine products, red meat and animal viscera, but zinc element is deficient in human body due to dietary imbalance, monophagia and other reasons. Once the zinc element is not enough to be taken by a human body, the appetite and the immune function are reduced, and even the problems of dysnoesia, fetal deformity and the like are caused. Zinc gluconate has the advantages of being non-toxic and easy to be absorbed by human body, so that the food, nutrient and medicine containing zinc gluconate are produced in large quantities, so as to effectively prevent and treat zinc deficiency. Unfortunately, however, not all zinc gluconate is consumed in a timely manner during its useful life and discarded at its recovery time due to widespread use and supply and demand. Expired zinc gluconate is usually disposed of as waste and improper disposal can introduce zinc ions into the environment. Excessive zinc ions can enter water environment, so that soil loses activity, plant growth is influenced, and great harm is caused to people and animals. Therefore, in order to avoid environmental pollution and waste of zinc resources, the recycling of expired zinc gluconate is urgently developed.
Disclosure of Invention
The invention provides a method for recycling overdue zinc gluconate, which is characterized in that black ZnO/C powder obtained by recycling overdue zinc gluconate is firstly recycled by a method of combining hydrothermal carbonization and high-temperature carbonization, the feasibility of the black ZnO/C powder serving as a negative electrode material of a lithium ion battery is investigated, and the secondary value of the overdue zinc gluconate is fully utilized.
A method for recycling overdue zinc gluconate comprises the following specific steps:
firstly, overdue zinc gluconate is added with water to prepare a zinc gluconate solution, then the zinc gluconate solution is transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, black particles are obtained after 5-7 hours of hydrothermal reaction, the black particles are pyrolyzed and carbonized for 1 hour in nitrogen atmosphere, cooled to room temperature, cleaned and dried to obtain black ZnO/C powder.
The overdue zinc gluconate is bottled oral liquid or solid powder, and comprises overdue zinc gluconate oral liquid or overdue zinc gluconate powder.
The concentration of the zinc gluconate solution is 0.003 g/mL-0.06 g/mL.
The temperature of the hydrothermal reaction is 180-200 ℃.
The temperature of pyrolysis carbonization is 750-850 ℃.
The black ZnO/C composite material recovered by the method is used as a lithium ion battery negative electrode active material, and the electrochemical lithium storage performance of the black ZnO/C composite material as the lithium ion battery negative electrode material is examined.
The invention has the beneficial effects that:
the invention develops a waste resource, namely a secondary use value of overdue zinc gluconate, firstly recovers the overdue zinc gluconate by a method of combining hydrothermal carbonization and high-temperature carbonization, uses the obtained black ZnO/C composite material as a lithium ion battery cathode active material, and inspects the feasibility of the black ZnO/C composite material as the lithium ion battery cathode active material. The method has the advantages of simple process and environmental protection, fully utilizes the secondary value of overdue zinc gluconate, and has positive contribution to the development of a circular economy mode and the environmental protection.
Drawings
FIG. 1 is an SEM image of a black ZnO/C material prepared in example 1 of the present invention;
FIG. 2 is an EDX spectrum of a black ZnO/C material prepared in example 2 of the present invention;
FIG. 3 is an XRD spectrum of a black ZnO/C material prepared in example 3 of the present invention;
FIG. 4 is a charge/discharge curve of a simulated lithium ion battery assembled with black ZnO/C material prepared in example 4 of the present invention;
FIG. 5 is a cycling stability curve for a simulated lithium ion battery assembled with black ZnO/C material prepared in example 5 of the present invention;
fig. 6 is a cyclic voltammogram of a simulated lithium ion battery assembled from black ZnO/C material prepared in example 6 of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
A method for recycling overdue zinc gluconate is characterized in that a black ZnO/C composite material is obtained by recycling overdue zinc gluconate by a method of combining hydrothermal carbonization and high-temperature carbonization, specifically, firstly, water is added into overdue zinc gluconate oral liquid to prepare a zinc gluconate solution with the concentration of 0.003g/mL, the zinc gluconate solution is transferred into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and undergoes hydrothermal reaction at 200 ℃ for 5 hours to obtain black particles, then the black particles are pyrolyzed and carbonized at 800 ℃ in a nitrogen atmosphere for 1 hour, cooled to room temperature, washed by water and then subjected to vacuum 70 hoursoAnd drying the C for 5 hours to obtain the black ZnO/C composite material.
The microstructure of the black ZnO/C composite material obtained by SEM test is shown in figure 1. As shown in figure 1, the black ZnO/C material is microscopically microspherical, the grain size is about 4.7-5.1 um, and the outer surface of each carbon microsphere is uniformly coated with a layer of zinc oxide nano-particles, wherein the grain size is about 100-400 nm.
Example 2
A method for recycling overdue zinc gluconate is characterized in that a method combining hydrothermal carbonization and high-temperature carbonization is adopted to recycle the overdue zinc gluconate to prepare a black ZnO/C composite material, and specifically, the overdue glucose is firstly recycledAdding water into zinc powder to prepare 0.06g/mL zinc gluconate solution, transferring the zinc gluconate solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 180 ℃ for 6h to obtain black particles, carrying out pyrolysis carbonization on the black particles at 750 ℃ in a nitrogen atmosphere for 1h, cooling to room temperature, washing with water, and carrying out vacuum 70oAnd C, drying for 5.5 h to obtain the black ZnO/C composite material.
The elemental composition of the black ZnO/C composite obtained in this example was tested using the EDX technique, as shown in fig. 2. As can be seen from FIG. 2, the ZnO/C composite material mainly contained C, Zn and O, and had no other impurity elements.
Example 3
A method for recycling overdue zinc gluconate is characterized in that a black ZnO/C composite material is obtained by recycling overdue zinc gluconate through a method of combining hydrothermal carbonization and high-temperature carbonization, specifically, overdue zinc gluconate particles are dissolved in water to prepare a 0.06g/mL zinc gluconate solution, the zinc gluconate solution is transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction at 200 ℃ for 7 hours to obtain black particles, then the black particles are pyrolyzed and carbonized at 850 ℃ in a nitrogen atmosphere for 1 hour, cooled to room temperature, cleaned by water and dried by a blast drier at 50 ℃ for 6 hours to obtain the black ZnO/C composite material.
The black ZnO/C composite crystalline phase obtained in this example was measured by XRD, as shown in FIG. 3. As can be seen from FIG. 3, the diffraction peak of zinc oxide is strong and sharp, corresponding to the XRD standard spectrum of zinc oxide, no impurity peak appears, indicating that the crystallinity of zinc oxide is high. In addition, two diffraction peaks corresponding to the (002) and (101) crystal planes of carbon, respectively, also appear at 2 θ = 23 ° and 43 °, which are wide and weak, indicating disorder and a low degree of graphitization of carbon.
Example 4
A method for recycling overdue zinc gluconate is characterized in that a black ZnO/C composite material is obtained by recycling overdue zinc gluconate by a method of combining hydrothermal carbonization and high-temperature carbonization, specifically, overdue zinc gluconate powder is dissolved in water and added with water to prepare 0.015g/mL zinc gluconate solution, and the zinc gluconate solution is transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining and placed in a hydrothermal reaction kettleCarrying out hydrothermal reaction at 180 ℃ for 5h to obtain black particles, then carrying out pyrolysis carbonization on the black particles at 800 ℃ for 1h in nitrogen atmosphere, cooling to room temperature, washing with water, and then carrying out forced air drying by using a blower dryer 60oAnd drying the C for 6h to obtain the black ZnO/C composite material.
The black ZnO/C composite material obtained in the embodiment is used as a negative electrode active material, and is assembled with a lithium foil to form a simulated lithium ion battery, and the electrochemical lithium storage performance of the simulated lithium ion battery is tested by a constant current charge/discharge method, as shown in FIG. 4, as can be seen from FIG. 4, the specific discharge capacities of the ZnO/C composite material during charge and discharge at current densities of 100mA/g, 200mA/g, 400mA/g, 800mA/g and 1000mA/g are 1247mAh/g, 468mAh/g, 386mA/g, 30mA/g and 243mA/g respectively, which indicates that the ZnO/C microsphere negative electrode has good lithium storage performance and rate capability.
Example 5
A method for recycling overdue zinc gluconate is characterized in that a method combining hydrothermal carbonization and high-temperature carbonization is adopted to recycle overdue zinc gluconate to prepare a black ZnO/C composite material, specifically, overdue zinc gluconate powder is dissolved in water to prepare a 0.04g/mL zinc gluconate solution, then the zinc gluconate solution is transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, hydrothermal reaction is carried out at 190 ℃ for 5 hours to obtain black particles, and then the black particles are pyrolyzed and carbonized at 850 ℃ for 1 hour under the nitrogen atmosphere; cooled to room temperature, washed with water and then vacuumed 50oAnd C, drying for 7h to obtain the black ZnO/C composite material.
The black ZnO/C composite material obtained in the embodiment is used as a negative electrode active material and is assembled with a lithium foil to form a circulation stability curve simulating a lithium ion battery, as shown in FIG. 5, as can be seen from FIG. 5, after 1000mA/g is circulated for 350 cycles, the reversible discharge specific capacity can be maintained at 350mAh/g, which indicates that the black spherical ZnO/C microsphere negative electrode has good circulation stability.
Example 6
A method for recycling overdue zinc gluconate is characterized in that a hydrothermal carbonization and high-temperature carbonization combined method is adopted to recycle overdue zinc gluconate powder to prepare a black ZnO/C composite material, specifically, the overdue zinc gluconate powder is dissolved in water to prepare a 0.05g/mL zinc gluconate solution, and then the zinc gluconate solution is transferred to a container with polytetrafluoroethyleneCarrying out hydrothermal reaction for 7h at 195 ℃ in an alkene-lined hydrothermal reaction kettle to obtain black particles, then carrying out pyrolysis carbonization on the black particles for 1h at 750 ℃ in a nitrogen atmosphere, cooling to room temperature, washing with water, and carrying out vacuum 70oAnd C, drying for 5h to obtain the black ZnO/C composite material.
The black ZnO/C composite material obtained in this example was used as a negative active material to assemble a lithium ion battery with a lithium foil, and a cyclic voltammetry curve was tested, as shown in fig. 6, it can be seen from fig. 6 that three weak oxidation peaks at 0.35V, 0.55V, and 0.7V were attributed to multi-step dealloying of a lithium-zinc alloy, a broad oxidation peak at 1.4V corresponded to the formation of ZnO, and a broad reduction peak at 0.7V corresponded to the reduction of ZnO to Zn and the formation of Li2The reaction of O, and the strong reduction peak close to 0V corresponds to the chemical reaction of the alloy of zinc and lithium, the corresponding electrochemical reaction formula is as follows:
ZnO + 2Li+ + 2e- ↔ Zn + Li2O （1）
Zn + xLi+ + xe- ↔ LixZn（x≤1） （2）
the ZnO/C negative electrode has good charge-discharge reversibility.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (2)

1. A method for recycling overdue zinc gluconate is characterized by comprising the following specific steps:
adding water into overdue zinc gluconate to prepare a zinc gluconate solution, carrying out hydrothermal reaction for 5-7 h to obtain a product, carrying out pyrolysis carbonization for 1h in a nitrogen atmosphere, cooling to room temperature, cleaning and drying to obtain a ZnO/C composite material; the overdue zinc gluconate is overdue zinc gluconate oral liquid or overdue zinc gluconate powder; the temperature of the hydrothermal reaction is 180-200 ℃; the temperature of pyrolysis carbonization is 750-850 ℃.
2. The method for recycling expired zinc gluconate according to claim 1, wherein the concentration of said zinc gluconate solution is in the range of 0.003g/mL to 0.06 g/mL.
CN201910359712.5A 2019-04-30 2019-04-30 Method for recycling overdue zinc gluconate Active CN110203963B (en)

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