CN118073701A - Regeneration and repair treatment method and application of waste zinc-nickel battery cathode material - Google Patents
Regeneration and repair treatment method and application of waste zinc-nickel battery cathode material Download PDFInfo
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- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008929 regeneration Effects 0.000 title claims abstract description 18
- 238000011069 regeneration method Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title claims description 7
- 230000001172 regenerating effect Effects 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 82
- 239000011787 zinc oxide Substances 0.000 claims description 40
- 239000002131 composite material Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 7
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 229910003962 NiZn Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 101150096185 PAAS gene Proteins 0.000 description 1
- -1 Polytetrafluoroethylene Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a regeneration and repair treatment method and application of a waste zinc-nickel battery negative electrode material in the technical field of zinc-nickel battery recovery, and mainly comprises the steps of treating a waste zinc-nickel battery negative electrode plate, regenerating and repairing the negative electrode material, and re-applying the repaired negative electrode material to a zinc-nickel battery. The regeneration and repair treatment method of the invention directly regenerates the active material on the basis of the waste zinc-nickel battery negative electrode sheet, has simple process, does not generate waste acid, is environment-friendly, reduces the treatment cost, is suitable for industrial expanded production, and provides a new scheme for recycling the waste zinc-nickel battery negative electrode.
Description
Technical Field
The invention relates to the technical field of zinc-nickel battery recovery, in particular to a regeneration and repair treatment method and application of a waste zinc-nickel battery negative electrode material.
Background
The zinc-nickel battery is used in the fields of vehicle starting or starting and stopping power supply, power battery, UPS, energy storage equipment and the like due to high safety, high energy density and power density, low cost and green environment protection. As the amount of zinc-nickel batteries increases, a large number of retired batteries are generated, which can cause serious pollution and resource waste if the batteries are not properly disposed. Therefore, the recovery and reuse of the waste zinc-nickel battery material and the elimination of pollution caused by the disposal of the waste batteries become an urgent task.
The zinc-nickel battery negative electrode comprises a copper grid, an active material (zinc oxide), an additive, an adhesive and a conductive agent. In the preparation process, the active material, the additive, the conductive agent, the adhesive and the water are mixed into uniform slurry, coated on the surface of the copper grid and pressed. In general, the zinc anode active material is recovered by dissolving the anode in acid liquor by an acid leaching method, filtering to remove impurities, adding a precipitant into the filtrate to obtain a precursor, and calcining the precursor to obtain zinc oxide. Pei Xiuzhong et al, by adopting the method, recovered and prepared zinc oxide ultrafine powder from waste dry batteries, and do not carry out test and research on the performance of the ultrafine powder; chai Xijuan et al recovered zinc from waste dry batteries and prepared nano zinc oxide powder, and did not conduct test study on its performance; the dywave adopts a direct precipitation method to recover and prepare zinc oxide from the waste dry battery, so that the antibacterial performance of the zinc oxide is researched; the dry batteries recovered in the method are all zinc-manganese primary batteries, and the recovery method of the zinc oxide regenerated by the waste zinc-nickel batteries is different from that of the waste zinc-nickel batteries. Cai Yunting et al propose the idea of recovering zinc oxide from waste zinc-nickel batteries by a precipitation method in the nickel-based battery recovery and zinc-nickel battery negative electrode recovery technology; lv Wenan a method for preparing zinc sulfate by treating the negative electrode of the waste zinc-nickel battery with sulfuric acid; xiaohua et al recovered calcium zincate or zinc aluminum talc from the negative electrode of zinc nickel batteries; in the past research work of our subject group Wang Dongming et al reported in recovery of zinc oxide and its re-use in waste Zinc Nickel batteries that zinc carbonate was first prepared by sodium carbonate precipitation, then calcined to prepare zinc oxide and its electrochemical properties were studied. Some products prepared by the method are zinc oxide fine powder used for antibacterial property research, some products only obtain zinc sulfate, calcium zincate or zinc aluminum talcum and the like, are not used for battery active materials to measure the electric properties of the battery active materials, only Wang Dongming and the like are used for researching and recovering zinc oxide and researching the electrochemical properties for zinc-nickel batteries, and test results show that the regenerated zinc oxide has no improvement on the electrochemical properties, the cycle life of the assembled zinc-nickel batteries is low, and the requirements of the current market on the service properties of the zinc-nickel batteries cannot be met.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for regenerating and repairing a waste zinc-nickel battery cathode material and application thereof, wherein the method is used for recovering and repairing active material zinc oxide in the waste zinc-nickel battery cathode, and the regenerated zinc oxide has excellent electrochemical performance by adopting a new process in the repairing process and is directly applied to a zinc-nickel battery.
The purpose of the invention is realized in the following way: a regeneration and repair treatment method for a waste zinc-nickel battery cathode material comprises the following steps:
(1) Discharging the waste zinc-nickel battery, disassembling the waste zinc-nickel battery to obtain a negative plate, immersing the negative plate in deionized water to remove alkaline electrolyte until the pH value of the solution is changed to be neutral, and drying the negative plate at 40-60 ℃;
(2) Calcining in air atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, calcining at high temperature to remove the binder and the conductive agent on the negative electrode plate, and stripping the negative electrode powder from the electrode plate;
(3) Soaking the cathode powder in 4mol L -1 hydrochloric acid solution, filtering to obtain a leaching solution, adding zinc sheets into the leaching solution, and filtering after the reaction is finished to obtain a filtrate; because the surface of the copper grid of the negative electrode current collector is oxidized, the stripping material contains copper compounds, the copper compounds react with acid, the leached solution contains copper ions, copper or copper compounds can not be used as active materials, zinc sheets are added to remove copper ions and other metal ions in the leachate, the other metal ions come from products after the reaction of additives and acid, the reaction activity is lower than that of zinc, and the copper compounds and the acid can be simultaneously replaced and removed, so that the purity of the repaired active materials is improved, and the electrochemical reaction activity is improved;
(4) Measuring various ion types and contents of the filtrate obtained In the step (3) by ICP-OES, wherein the concentration of Zn 2+ In the recovery liquid is 62909.6mg/L, the concentration of Cu 2+ is 24.5mg/L, the concentration of Bi 3+ is 0.047mg/L, the concentration of In 3+ is 0.039mg/L, the concentration of Ga 3+ is 0.026mg/L, and the proportion of other ions is extremely small compared with zinc ions, so that the existence of other ions is not considered In the regeneration process;
(5) Setting the reaction temperature to be 40-60 ℃, slowly adding ammonium bicarbonate solution into the filtrate to prepare basic zinc carbonate, keeping the reaction system in a stirring state, aging for 1-2 hours after the dripping is completed, and washing the obtained product with deionized water to obtain basic zinc carbonate;
(6) Bismuth nitrate and concentrated nitric acid according to the proportion of 1:1.22, dissolving bismuth nitrate in nitric acid to obtain bismuth nitrate solution, adding the basic zinc carbonate obtained in step (5) into the bismuth nitrate solution, stirring while adding to uniformly mix, drying the mixture, transferring the mixture into a tube furnace, calcining for 1h at the temperature of 300 ℃ at 5 ℃/min and then at the temperature of 830 ℃ at 5 ℃/min under the nitrogen atmosphere to obtain the zinc oxide@bismuth oxide composite material, wherein the bismuth oxide content is 3% of the mass percentage of the obtained ZnO@Bi 2O3 composite material.
The invention further aims to provide the ZnO@Bi 2O3 composite material obtained by the regeneration and repair treatment method as a negative electrode material, and the composite material is assembled with a nickel positive electrode to form a zinc-nickel battery, wherein a sulfonated film is a diaphragm, an electrolyte is KOH gel electrolyte, and the zinc-nickel soft-package battery is prepared and tested for electrochemical properties such as energy density, power density, cycle stability and the like.
Compared with the prior art, the invention has the beneficial effects that:
Firstly, the regeneration and repair treatment method directly regenerates the active material on the basis of the waste zinc-nickel battery negative electrode sheet, generates no waste acid, is environment-friendly, and reduces the treatment cost.
Secondly, the ZnO@Bi 2O3 composite material prepared by the regeneration repair treatment method has high energy density, power density and long cycle life when being used for preparing a zinc-nickel battery by using the negative electrode and the nickel positive electrode, and the energy density can still be maintained to be 155 Wh.kg -1 when the cycle number of the battery reaches 3125.
Thirdly, the regeneration and repair treatment method has simple flow, low cost and no need of complex equipment, is suitable for industrial expansion production, and provides a new scheme for recycling the negative electrode of the waste zinc-nickel battery.
Drawings
FIG. 1 is an SEM image of repaired zinc oxide obtained by the regeneration repair treatment method of the present invention.
Fig. 2 is a charge-discharge curve diagram of a zinc-nickel battery assembled by using the zno@bi 2O3 composite material obtained by the regeneration repair treatment method of the present invention as a negative electrode and a nickel positive electrode.
Fig. 3 is a cycle life chart of a zinc-nickel battery assembled by using the ZnO@Bi 2O3 composite material obtained by the regeneration repair treatment method as a negative electrode and a nickel positive electrode.
Detailed Description
Example 1: regeneration and repair of waste zinc-nickel battery cathode material
Step one, pretreatment of a waste zinc-nickel battery negative plate:
(1) Placing the negative electrode sheet obtained by discharging and disassembling into a beaker filled with deionized water, immersing for 24 hours, changing water once every 8 hours to remove alkaline electrolyte, drying at 40-60 ℃, removing lugs and diaphragms, transferring the negative electrode sheet into a tubular furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under air atmosphere, calcining for 2 hours, wherein the adhesive on the original waste zinc sheet is a high polymer material, the conductive agent is carbon black, and the negative electrode material can be easily stripped from the surface of a current collector to obtain negative electrode powder and a current collector after calcining;
(2) 10g of negative electrode powder is taken to be placed into 100mL of 4mol/L hydrochloric acid solution for soaking, after the reaction is finished, clear green filtrate is obtained by filtering, 3g of zinc sheet is added to remove copper ions and excessive hydrochloric acid in the solution, colorless clear transparent leaching solution is obtained by filtering, and the type and the content of each ion in the filtrate are measured by ICP-OES (inductively coupled plasma-optical emission spectrometry) for repairing and regenerating the negative electrode active material.
Repairing and regenerating the anode active material:
Weighing 12.76g of ammonium bicarbonate, dissolving in 110mL of deionized water to obtain a solution, slowly dripping the ammonium bicarbonate solution into the filtrate obtained in the first step, keeping the reaction system uniformly stirred, controlling the reaction temperature to be 40-60 ℃, stopping stirring after the reaction is finished, aging for 2 hours at 40-60 ℃, centrifuging, washing and drying to obtain basic zinc carbonate; weighing 0.4g of bismuth nitrate, dissolving in nitric acid to obtain bismuth nitrate solution, adding basic zinc carbonate powder into the bismuth nitrate solution under the condition of stirring, uniformly mixing, drying, transferring into a tube furnace for calcination, heating to 300 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere for calcination for 1h, continuously heating to 830 ℃ at a heating rate of 5 ℃/min for calcination for 2h, and naturally cooling to room temperature to obtain the ZnO@Bi 2O3 composite material.
The scanning electron microscope image of the prepared ZnO@Bi 2O3 composite material is shown in figure 1, and irregular particles with the particle size of about 2 microns can be observed as the product morphology.
The ZnO@Bi 2O3 composite material is applied to a zinc-nickel battery:
The ZnO@Bi 2O3 composite material, carbon nanofiber and Polytetrafluoroethylene (PTFE) are prepared according to the mass ratio of 25:3: mixing uniformly to paste state at 0.468, uniformly coating on a tinned copper mesh, drying and tabletting to obtain a zinc negative plate; the nickel positive plate is prepared from Ni 0.99Co0.01(OH)2/carbon nanofiber, nickel powder and PTFE according to the mass ratio of 10:1:0.72, uniformly mixing to slurry, uniformly coating on foam nickel, drying and tabletting to prepare a nickel positive plate; and assembling the zinc negative plate and the nickel positive plate into a zinc-nickel battery, wherein the sulfonated film is a diaphragm, the electrolyte is a PAAS gel solution of 6M KOH+1M LiOH+saturated ZnO, and the prepared zinc-nickel battery is subjected to charge and discharge test, the charge and discharge current is 20mA cm -2, the charge cut-off voltage is 2.15V, the discharge cut-off voltage is 1.0V, and the electrochemical performances such as energy density, cycle stability and the like are tested.
The charging and discharging curve is shown in figure 2, and the charging and discharging curve is smooth and regular, and has good reversibility.
Fig. 3 is a graph showing the cycle life of a zinc-nickel battery at a charge-discharge current density of 20ma·cm -2, wherein the energy density can reach 172.2wh·kg -1, and when the cycle number reaches 3125 times, the energy density can still maintain 155wh·kg -1, about 90% of the initial value, and a long cycle life is exhibited.
Comparative example 1: electrochemical performance of non-regenerated ZnO@Bi 2O3 composite material
In the previous work of the subject group, a method for synthesizing a ZnO@Bi 2O3 composite material by high-temperature solid phase is developed, and the electrochemical properties of the ZnO@Bi 2O3 composite material prepared by regeneration and a NiZn battery assembled by a negative electrode prepared by non-regenerated ZnO@Bi 2O3 composite material are shown in table 1. By comparison, the electrochemical performances of the two materials are close, which shows that the ZnO@Bi 2O3 composite material obtained by the method for regenerating and repairing the waste zinc-nickel battery cathode material has excellent electrochemical performances.
Table 1 electrochemical Properties of NiZn cell assembled with ZnO@Bi 2O3 composite material prepared by regeneration and non-re-composite material
Comparative example 2: electrochemical performance of regenerated zinc oxide
The subject group Wang Dongming et al reported in the article "recovery of Zinc oxide from waste Zinc Nickel batteries and its re-use" that sodium carbonate was used for precipitation to prepare Zinc carbonate, calcination to prepare ZnO and study its electrochemical properties. Table 2 compares the electrochemical performance of the fabricated negative electrode assembled NiZn cell and the regeneratively fabricated ZnO@Bi 2O3 composite material. The performance of the composite material regenerated by the new technology is far superior to that of ZnO regenerated by the new technology, which shows that the method has superiority.
Table 2 electrochemical Properties of regenerated ZnO@Bi 2O3 composite Material and regenerated ZnO assembled NiZn Battery
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (9)
1. The regeneration and repair treatment method for the waste zinc-nickel battery cathode material is characterized by comprising the following steps of:
(1) Discharging and disassembling the waste zinc-nickel battery to obtain a negative plate;
(2) Removing the binder and the conductive agent on the negative electrode plate by high-temperature calcination, and stripping the negative electrode powder from the electrode plate;
(3) Leaching the leaching solution by adopting acid leaching cathode powder and filtering to obtain leaching solution, adding zinc sheets into the leaching solution, and filtering after the reaction is finished to obtain filtrate;
(4) Measuring various ion types and contents of the filtrate obtained in the step (3);
(5) Setting a reaction temperature, adding ammonium bicarbonate solution into the filtrate to prepare basic zinc carbonate, and keeping a reaction system in a stirring state;
(6) And (3) mixing bismuth nitrate solution with the basic zinc carbonate obtained in the step (5), drying, and calcining to obtain the zinc oxide@bismuth oxide composite material.
2. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: and immersing the negative electrode piece obtained by disassembling the waste zinc-nickel battery in deionized water to remove alkaline electrolyte until the pH value of the solution is changed to be neutral, and drying the negative electrode piece at 40-60 ℃.
3. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the calcining conditions in the step (2) are as follows: calcining under air atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h ℃.
4. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the acid in the step (3) is 4 mol L -1 hydrochloric acid solution.
5. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the determination in step (4) uses ICP-OES to determine the kinds and contents of various ions in the filtrate.
6. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the reaction temperature in the step (5) is 40-60 ℃.
7. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the bismuth nitrate solution in the step (6) is bismuth nitrate and concentrated nitric acid according to the mass ratio: 1:1.22, wherein the calcination mechanism is to calcine 1h at 5 ℃/min to 300 ℃ and then calcine 2h at 5 ℃/min to 830 ℃.
8. The method for regenerating and repairing the anode material of the waste zinc-nickel battery according to claim 1, which is characterized by comprising the following steps: the bismuth oxide content in the step (6) is 3% of the mass percentage of the obtained zinc oxide@bismuth oxide composite material.
9. The zinc oxide@bismuth oxide composite material obtained by the method for regenerating and repairing the waste zinc-nickel battery negative electrode material according to any one of claims 1-8 is directly applied to a zinc-nickel battery as a negative electrode material.
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| CN202410394097.2A CN118073701A (en) | 2024-04-02 | 2024-04-02 | Regeneration and repair treatment method and application of waste zinc-nickel battery cathode material |
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