CN112614993A - Ppy modified water system zinc-cobalt battery anode material - Google Patents
Ppy modified water system zinc-cobalt battery anode material Download PDFInfo
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- CN112614993A CN112614993A CN202011434039.6A CN202011434039A CN112614993A CN 112614993 A CN112614993 A CN 112614993A CN 202011434039 A CN202011434039 A CN 202011434039A CN 112614993 A CN112614993 A CN 112614993A
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- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims abstract description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002060 nanoflake Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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- H—ELECTRICITY
- 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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a ppy modified water system zinc-cobalt battery anode material. The anode material is nano flaky cobalt phosphate modified by ppy growing on a three-dimensional substrate, the cathode is a zinc sheet, and the electrolyte is potassium hydroxide with a certain concentration and a soluble zinc salt aqueous solution. Compared with the prior art, the transition metal phosphate material is applied to a water system zinc-cobalt battery system for the first time, the cobalt phosphate prepared in situ on the foamed nickel has a nano sheet structure with a high specific surface area, has high specific capacity and good cycling stability, the capacity of the material is further improved through ppy coating, and the preparation process is simple and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of high-energy water-based batteries, and particularly relates to a high-energy water-based zinc-cobalt battery positive electrode material.
Background
With the progress of the human society, the popularization of electronic equipment and the rapid popularization of low-carbon and environment-friendly electric traffic, the demand of human beings on secondary batteries is increasing. The secondary battery is a high-efficiency energy storage device, can realize repeated charge and discharge and recycling, and has the characteristics of small pollution, low cost and the like compared with a primary battery. The major secondary battery technologies today include nickel-chromium batteries, nickel-hydrogen batteries, lead-acid batteries, lithium ion batteries, and the like. Nickel-chromium batteries and lead-acid batteries appear earlier, but have the disadvantages of lower capacity and shorter service life, and heavy metals in the batteries cause huge pollution to the environment, so the development prospect is limited. The lithium ion battery is the most widely applied battery at present, but the demand for lithium is rapidly increased at the same time, the global storage capacity of lithium is limited, the price is rapidly increased, the low cost requirement is not met, and the organic electrolyte used by the lithium ion battery is flammable and has great safety problem.
The aqueous zinc-cobalt battery is a secondary battery which is recently emerging, has higher battery capacity and longer service life than a nickel-chromium battery and a lead-acid battery, and does not cause great harm to the environment due to the absence of heavy metals. Compared with the lithium ion battery, the zinc storage capacity is richer than that of lithium, the cost is much lower than that of the lithium ion battery, the electrolyte is the aqueous solution of potassium hydroxide, combustion and explosion cannot be caused, the safety is relatively high, and the zinc storage battery has high potential value in the large-scale energy storage field. The cobalt phosphate nanosheet prepared by the hydrothermal method has a large specific surface area, enhances ion accessibility, shortens an ion expansion approach, accelerates electron conduction, leads to higher specific capacity, reduces surface capacity loss and leads to longer cycling stability.
Disclosure of Invention
The invention aims to provide an aqueous zinc-cobalt battery. The battery comprises a battery anode material, a battery cathode material and an electrolyte solution. The positive electrode material of the battery is a ppy modified nano flaky cobalt phosphate material which uniformly grows on a three-dimensional substrate, and has the characteristics of rich raw materials, good stability, high specific capacity and the like. The method has mild reaction conditions and low cost, and can be applied to large-scale production. The negative electrode material of the battery is a zinc sheet, and the electrolyte is potassium hydroxide and soluble zinc salt aqueous solution with certain concentration, so that the problems of corrosion and passivation of the battery can be effectively solved.
The water-based zinc-cobalt battery comprises a battery anode material, a cathode material and electrolyte, wherein the anode material is nano flaky cobalt phosphate growing on a three-dimensional substrate, the cathode material is a zinc sheet, and the electrolyte comprises potassium hydroxide with a certain concentration and a soluble zinc salt aqueous solution.
The anode material is cobalt phosphate material which is Co3(PO4)2。
The preparation method of the anode material of the water system zinc-cobalt battery comprises the following steps:
mixing cobalt salt and phosphate at room temperature, dissolving in deionized water, transferring the obtained solution into a hydrothermal kettle containing a three-dimensional substrate material for hydrothermal reaction, cooling, taking out the foamed nickel, washing and drying to obtain the cobalt phosphate material growing on the three-dimensional substrate.
The concentration of cobalt salt and phosphate used in the preparation of the cathode material is 0.0001-0.5 mol/L.
The cobalt salt used in the preparation of the cathode material comprises cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate.
The phosphate used in the preparation of the cathode material comprises ammonium dihydrogen phosphate, potassium dihydrogen phosphate or sodium dihydrogen phosphate.
When the positive electrode material is prepared, the volume of a solution is 50-90% of the volume of a high-pressure reaction kettle.
The hydrothermal reaction temperature conditions are as follows: reacting for 1-36 h at 100-200 ℃.
The anode material is dried for 1-12 hours at 50-80 ℃ during preparation, and the anode material of the water-based zinc-cobalt battery is obtained.
The three-dimensional substrate used in the preparation of the cathode material comprises any one of carbon paper, foamed nickel, a titanium alloy net or a stainless steel net.
The positive electrode material can also be a PPy post-treatment product obtained by soaking the positive electrode material in a mixed solution containing p-toluenesulfonic acid, pyrrole monomer and ammonium persulfate, and soaking for 1-20h after ultrasonic dispersion; in the mixed solution, the mass ratio of the p-toluenesulfonic acid to the pyrrole monomer to the ammonium persulfate is 1: 5: 3; the mass concentration of the mixed solution is 0.0001-0.1 mol/L; the solvent used in the mixed solution includes water or ethanol.
The negative electrode material is a zinc sheet, a zinc foil or zinc powder.
The electrolyte comprises potassium hydroxide and soluble zinc salt at certain concentration.
The concentration of the potassium hydroxide in the electrolyte is 0.1-10M.
The types of the zinc salt in the electrolyte comprise zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
Compared with the prior art, the invention has the following advantages:
the water system zinc-cobalt battery consists of a battery anode, a battery cathode and electrolyte. According to the invention, cobalt phosphate is firstly applied to the research of a zinc-cobalt battery, and the nanosheet-loaded nanosheet-shaped cobalt phosphate composite material uniformly grown on the three-dimensional substrate is synthesized by the anode through a one-step hydrothermal method, so that the nanosheet-loaded nanosheet-shaped cobalt phosphate composite material has a large specific surface area. The material has rich raw materials, good stability and high specific capacity, thereby showing excellent electrochemical performance. The cobalt phosphate material disclosed by the invention has extremely high capacity, and the reduction peak value can reach 100mA/cm under a certain sweeping speed2In the above-mentioned manner,and the reduction peak value is also continuously and obviously improved along with the increase of the concentration. The peak value after the compounding and the PPy treatment is improved by more than one time, wherein the peak value after the compounding is as high as 280mA/cm2The peak value after PPy treatment can reach 200mA/cm2The capacity of these peak transitions is much higher than the capacity of materials made by other processes in the same field.
Drawings
FIG. 1 shows that the reactant in example 1 is (a) Co3(PO4)2-1（b）Co3(PO4)2-2（c）Co3(PO4)2-3（d）Co3(PO4)2SEM image of cobalt phosphate grown on foamed nickel substrate under 4 conditions.
FIG. 2 shows that the reactant in example 1 is (a) Co3(PO4)2-1（b）Co3(PO4)2-2（c）Co3(PO4)2-3（d）Co3(PO4)2CV plot of cobalt phosphate grown on foamed nickel substrate under conditions of 4.
FIG. 3 is a graph of CV for cobalt phosphate grown on a foamed nickel substrate and treated with PPy for various lengths of time in example 3.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it.
Example 1
Ammonium dihydrogen phosphate (0.4 mM) and cobalt nitrate (0.6 mM) were dissolved in 80ml of deionized water, and the solution was stirred at room temperature to obtain a pink solution, which was transferred to a container containing nickel foam (2X 4 cm)2) Carrying out hydrothermal reaction in the hydrothermal kettle at 120 ℃ for 6 hours, cooling, taking out the foamed nickel, washing for multiple times, and drying in a 60 ℃ oven. Obtaining cobalt phosphate material (marked as Co) growing on the foamed nickel substrate3(PO4)2-1）。
The method is the same as the above correction, only ammonium dihydrogen phosphate and cobalt nitrate are respectively adjusted to 0.8mM and 1.2mM, and the obtained product is grown on the foam nickel baseCobalt phosphate material of the bottom (labeled as Co)3(PO4)2-2）。
Ammonium dihydrogen phosphate and cobalt nitrate were adjusted to 1.2mM and 1.8mM, respectively, and the resulting product was a cobalt phosphate material (labeled Co) grown on a foamed nickel substrate3(PO4)2-3）。
Ammonium dihydrogen phosphate and cobalt nitrate were adjusted to 1.6mM and 2.4mM, respectively, and the resulting product was a cobalt phosphate material (labeled Co) grown on a foamed nickel substrate3(PO4)2-4）。
FIG. 1 (a) shows a sample Co of cobalt phosphate prepared in example 1 of the present invention3(PO4)2SEM picture of-1. As can be seen, the nano flaky cobalt phosphate is successfully grown on the foamed nickel substrate by the one-step hydrothermal method, and the nano flaky structures can be uniformly and compactly arranged on the foamed nickel. FIG. 1 (b) shows the cobalt phosphate sample Co3(PO4)2SEM image of-2, it can be seen that the morphology is very similar to that of FIG. 1 (a), except that the sheet structure is coarser and more compact than before, further demonstrating that this method can synthesize nanoplatelets. FIGS. 1 (c) and (d) are each a sample of cobalt phosphate Co3(PO4)2-3、Co3(PO4)2SEM image of-4, from which it can be seen that the previous nano-platelet structure still exists, but the platelet structure grows into a plate shape due to the excessive concentration.
FIG. 2 is a cyclic voltammogram of four samples of example 1, and Co can be seen3(PO4)21 the reduction peak value of the sample at the sweep speed can reach 100mA/cm2Shows higher capacity, and the reduction peak value of the sample is continuously increased along with the increase of the concentration, and is also increased in Co3(PO4)2The peak value of-4 reaches 300mA/cm2The high-capacity lithium ion battery has extremely high capacity and great potential value.
Example 2
Sample Co of example 13(PO4)2-1 soaking in a PPy-containing mixed solution for post-treatment, in particularDissolving 2mg of p-toluenesulfonic acid into 3mL of ethanol, adding 5mg of pyrrole monomer to prepare solution A, dissolving 6mg of ammonium persulfate into 2mL of deionized water to obtain solution B, slowly and dropwise adding the solution B into the solution A, and performing ultrasonic treatment for 30 minutes to obtain a sample Co of example 13(PO4)2-1, soaking in the ultrasonic mixed solution for 9 hours and 12 hours, and taking out to obtain sample Co3(PO4)2PPy-9h and Co3(PO4)2PPy-12, the test method being exactly the same as in example 1.
FIG. 3 is a cyclic voltammogram of the sample of example 3, and it can be seen that the current density corresponding to the reduction peak of the original sample at the same sweep rate is substantially the same as that of the original sample of example 2, and the reduction peak of the sample treated for 9h after soaking for PPy reaches 150mA/cm2After 12h, the post-treatment time reaches 200mA/cm2The capacity of the sample is respectively increased to 1.5 times and 2 times of the original sample capacity, and the obvious increase of the sample capacity by the post-treatment also has potential value.
Claims (9)
1. The positive electrode material is nano flaky cobalt phosphate growing on a three-dimensional substrate, the negative electrode material is a zinc sheet, and the electrolyte is potassium hydroxide or a soluble zinc salt aqueous solution with a certain concentration.
2. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 1, wherein the chemical formula of the nano-flake cobalt phosphate is Co3 (PO4)2。
3. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 2, wherein the preparation method of the aqueous zinc-cobalt battery positive electrode material comprises the following steps:
mixing cobalt salt and phosphate at room temperature, dissolving the mixture in deionized water, transferring the obtained solution into a hydrothermal kettle containing a three-dimensional substrate material for hydrothermal reaction, cooling, taking out foamed nickel, washing and drying to obtain a cobalt phosphate anode material growing on the three-dimensional substrate, soaking the obtained cobalt phosphate anode material in a mixed solution containing p-toluenesulfonic acid, pyrrole monomers and ammonium persulfate, and soaking for 1-20 hours after ultrasonic dispersion to obtain the water system zinc-cobalt battery anode material.
4. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 3, wherein the cobalt salt comprises any one of cobalt nitrate, cobalt chloride, cobalt sulfate, or cobalt acetate; the phosphate comprises ammonium dihydrogen phosphate, potassium dihydrogen phosphate or sodium dihydrogen phosphate; the concentrations of the cobalt salt and the phosphate are both 0.0001-0.5 mol/L.
5. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 3, wherein the hydrothermal reaction temperature and time are as follows: reacting for 1-36 h at 100-200 ℃.
6. The ppy modified water system zinc-cobalt battery cathode material of claim 3, wherein the three-dimensional substrate comprises carbon paper, foamed nickel, titanium alloy mesh or stainless steel mesh.
7. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 3, wherein the mass ratio of the p-toluenesulfonic acid, the pyrrole monomer and the ammonium persulfate in the mixed solution is 1: 4-5: 2-3; the concentration of the mixed solution is 0.0001-0.1 mol/L; the solvent used in the mixed solution includes water or ethanol.
8. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 7, wherein the mass ratio of the p-toluenesulfonic acid, the pyrrole monomer and the ammonium persulfate in the mixed solution is 1: 5: 3; the concentration of the mixed solution is 0.0001-0.1 mol/L; the solvent used in the mixed solution includes water or ethanol.
9. The ppy modified aqueous zinc-cobalt battery positive electrode material as claimed in claim 1, wherein the concentration of potassium hydroxide in the electrolyte is 0.1-10M, and the soluble zinc salt aqueous solution comprises any one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
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