CN115513406A - Zinc ion battery cathode, preparation method thereof and zinc ion battery - Google Patents
Zinc ion battery cathode, preparation method thereof and zinc ion battery Download PDFInfo
- Publication number
- CN115513406A CN115513406A CN202211214694.XA CN202211214694A CN115513406A CN 115513406 A CN115513406 A CN 115513406A CN 202211214694 A CN202211214694 A CN 202211214694A CN 115513406 A CN115513406 A CN 115513406A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- negative electrode
- zinc
- zinc ion
- dimensional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000016 photochemical curing Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 238000010146 3D printing Methods 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011267 electrode slurry Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- 238000000280 densification Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 150000004291 polyenes Chemical class 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920006295 polythiol Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229920006305 unsaturated polyester Polymers 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000007639 printing Methods 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000007600 charging Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010425 computer drawing Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of secondary batteries, and particularly discloses a zinc ion battery metal cathode, a preparation method thereof and a zinc ion battery, wherein the zinc ion battery comprises the following steps: s1, forming the negative electrode slurry into a three-dimensional zinc ion battery negative electrode blank through photocuring 3D printing; s2, sequentially degumming and densifying and sintering the three-dimensional zinc ion battery negative electrode blank; and S3, reducing the sintered product to obtain a three-dimensional porous structure containing zinc metal, namely the zinc ion battery cathode. The negative electrode material prepared by the invention has good conductivity and large specific surface area, realizes the controllable manufacture of the three-dimensional metal negative electrode, can effectively inhibit the growth of zinc dendrites, improves the safety performance of the battery and prolongs the service life of the battery. In addition, the porous structure of the 3D printing negative electrode improves the diffusion speed of ions, so that the battery has higher ionic and electronic conductivity.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a zinc ion battery cathode, a preparation method of the zinc ion battery cathode, and a zinc ion battery.
Background
The water system zinc ion battery has high safety, low cost, simple process and high theoretical capacity of zinc metal (820 mAh g) -1 ) And the like, are considered as important choices for next-generation rechargeable batteries.
However, the application of the current zinc ion battery still cannot be popularized because of two reasons: the volume expansion problem of the negative electrode in the charging and discharging process and the problem that the dendrite grows to pierce through the diaphragm to cause short circuit in the battery and further lose efficacy. Therefore, it is a research focus in the field to inhibit dendritic growth during charging and discharging of a zinc ion battery while ensuring high coulombic efficiency. In order to overcome the defects of the existing water system zinc ion battery material, a preparation process of a three-dimensional structure water system zinc ion battery cathode material is urgently needed.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a zinc ion battery cathode, a preparation method thereof and a zinc ion battery, and aims to solve the problem of dendritic crystal growth in a water-based zinc ion battery and improve the ionic and electronic conductivity of the zinc ion battery.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a negative electrode of a zinc ion battery, comprising the steps of:
s1, forming the negative electrode slurry into a three-dimensional zinc ion battery negative electrode blank through photocuring 3D printing;
s2, sequentially degumming and densifying and sintering the three-dimensional zinc ion battery negative electrode blank;
and S3, reducing the sintered product to obtain a three-dimensional porous structure containing zinc metal, namely the zinc ion battery cathode.
Preferably, in step S2, the three-dimensional zinc ion battery negative electrode blank is sequentially degummed, densified and sintered, specifically: carrying out gradient sintering on the three-dimensional zinc ion battery cathode blank under the air condition, wherein the temperature is 400-600 ℃, and fully pyrolyzing the photosensitive resin; then the blank body without the photosensitive resin is densified and sintered under the condition of inert gas, and the temperature is 900-1200 ℃.
As a further preferable mode, the preparation method of the negative electrode slurry comprises: and uniformly mixing the negative active material powder with the photosensitive resin, the thickening agent and the photoinitiator to uniformly disperse the negative active material powder.
Further preferably, the negative electrode paste includes 30 to 90wt% of a negative electrode active material, 10 to 70wt% of a photosensitive resin, 0 to 20wt% of a thickener, and 0 to 3wt% of a photoinitiator.
More preferably, the negative active material is zinc oxide powder, the thickener is one or a mixture of several of polyurethane, polyacrylate, polyoxyethylene and cellulose thickeners, and the photosensitive resin is one or a mixture of several of acrylated epoxy resin, unsaturated polyester, polyurethane and polythiol/polyene photocuring resin.
Further preferably, in step S3, the sintered product is partially or completely reduced by thermal reduction or electrochemical reduction.
Further preferably, in step S1, the photo-curing 3D printing is a stereo photo-curing or digital photo-processing process.
According to a second aspect of the invention, a zinc ion battery cathode is provided, which is prepared by the preparation method.
According to a third aspect of the present invention, there is provided a zinc ion battery comprising the above zinc ion battery negative electrode.
As further preferable, a positive electrode material including nickel oxide, activated carbon, manganese oxide, vanadium oxide, prussian blue analog, organic compound, and the like, and an electrolytic solution including potassium hydroxide solution, zinc sulfate solution, and the like are also included.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. according to the invention, the negative electrode with a three-dimensional porous structure is prepared through photocuring, and zinc ions are induced to deposit at a large internal specific surface area, so that dendritic crystals originally growing perpendicular to the diaphragm are changed into dendritic crystals growing parallel to the diaphragm, and short circuit and failure caused by the dendritic crystals can be effectively avoided. Meanwhile, the three-dimensional structure is beneficial to improving the diffusion speed of ions, so that the battery has higher ionic and electronic conductivity, the growth of zinc dendrites is effectively inhibited, the safety performance and the service life of the battery are improved, and the preparation method is a more safe and excellent secondary battery cathode preparation method.
2. In the prior art, a solid lithium ion battery is prepared by photocuring, but the residual resin can affect the conductivity, and a metal electrode cannot be produced independently, so that the problem of poor conductivity exists. Aiming at the zinc ion battery, the three-dimensional cathode blank is formed by photocuring, and meanwhile, the processes of degumming and sintering are combined, so that the printing of the metal cathode is realized, and the conductivity is improved.
3. According to the invention, degumming and densification sintering processes are designed, and by designing degumming temperature, the rapid decomposition of resin is ensured, the residue of the resin is removed, a pure metal cathode is obtained, and the conductivity is improved; meanwhile, the densification sintering temperature is designed to improve the mechanical strength of the blank body, avoid the situation that the mechanical strength of the blank body is insufficient due to too low temperature, collapse of the structure occurs under the working condition, and avoid the situation that the blank body excessively shrinks due to too high temperature.
4. The invention designs the cathode slurry, and obtains the zinc ion battery metal cathode material with high conductivity and high mechanical strength by adjusting the proportion of the cathode active material powder and the photosensitive resin.
Drawings
Fig. 1 (a) - (d) are schematic structural diagrams of a three-dimensional zinc-ion battery negative electrode blank according to an embodiment of the invention;
FIG. 2 shows a sintered ZnO green body and an electroreduced 3D zinc cathode according to an embodiment of the present invention;
fig. 3 (a) - (c) are ac impedance spectra of the battery system before, during and after electrochemical reduction according to the embodiment of the present invention;
FIG. 4 shows an embodiment NH of the present invention 4 V 4 O 10 A charge-discharge curve of the/3D Zn battery is 0.1A/g;
FIG. 5 is a flow chart of a method for preparing a zinc ion battery cathode according to an embodiment of the invention
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the zinc ion battery cathode provided by the embodiment of the invention, as shown in fig. 5, comprises the following steps:
s1, forming a three-dimensional zinc ion battery blank by using the negative electrode slurry through a photocuring 3D printing technology according to a zinc ion battery three-dimensional design model preset by a computer, as shown in figure 1.
Preferably, the negative electrode slurry comprises 30wt% -90 wt% of negative electrode active material, 10wt% -70 wt% of photosensitive resin, 0-20 wt% of thickening agent/dispersing agent and 0-3 wt% of photoinitiator, and the preparation method comprises the following steps: and uniformly mixing the negative active material powder with the photosensitive resin, the thickening agent and the photoinitiator to uniformly disperse the active material powder.
Specifically, the negative active material comprises zinc oxide powder, the thickening agent comprises one or a mixture of several of polyurethane, polyacrylate, polyoxyethylene and cellulose thickening agents, and the photosensitive resin comprises one or a mixture of several of acrylated epoxy resin, unsaturated polyester, polyurethane and polythiol/polyene photocuring resin.
Specifically, the photocuring 3D printing technology includes stereo photocuring (SL) and Digital Light Processing (DLP) processes.
S2, placing the printed battery cathode blank into a sintering furnace to sequentially carry out degumming and densification sintering;
preferably, the printed and molded zinc ion battery cathode is placed into a muffle furnace during degumming, and gradient sintering is carried out under the air condition, wherein the temperature range is 400-600 ℃, so that the photosensitive resin is fully pyrolyzed. The material without resin is put into a muffle furnace again, and densification sintering is carried out under the condition of air or inert gas, wherein the temperature range is 900-1200 ℃, so as to improve the mechanical strength. Preferably, gradient slow sintering is adopted to ensure that the shrinkage deformation of the green body is small and the structure is stable in the sintering process.
And S3, carrying out partial reduction or complete reduction on the sintered product by adopting thermal reduction or electrochemical reduction to obtain a three-dimensional porous structure containing zinc metal.
The invention also provides a zinc ion battery, and the zinc ion battery is formed by assembling the prepared zinc ion battery cathode, the anode material and the electrolyte together.
Specifically, the positive electrode material includes nickel oxide, activated carbon, manganese oxide, vanadium oxide, prussian blue analog, organic compound, and the like, and the electrolyte includes potassium hydroxide solution, zinc sulfate solution, and the like.
The invention combines the photocuring 3D printing technology, solves the problem of dendritic crystal growth in the water-based zinc ion battery through the advanced electrode structure design, and improves the performance of the energy storage equipment. The 3D printing technology has a high degree of freedom in structural design, and electrodes of complex geometry can be obtained by computer drawing. And the technology can be extended to a wide range of materials such as polymers, metals, metal oxides, carbon materials, ceramics, and the like. The highly automated manufacturing process and convenient synthesis route reduce the manufacturing cost of commercial electrodes compared to conventional electrode manufacturing processes. Meanwhile, the preparation method and the preparation conditions are controlled to obtain the negative electrode material for the zinc ion battery with high capacity, high multiplying power and cycle performance, which has important significance for promoting the development of the zinc ion battery with long service life, solving the problem of energy shortage and the like.
The following are specific examples:
example 1
Preparing a zinc ion battery, comprising the following steps:
the method comprises the following steps: mixing 21g of zinc oxide powder (the diameter of the powder is 10-100 mu m), 9g of photosensitive resin 1, 6-hexanediol diacrylate (HDDA) and 0.27g of photoinitiator diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus (TPO) to obtain printing slurry;
step two: putting the mixed slurry into a planetary ball mill, and uniformly mixing (the rotating speed is 250rpm, and the time is 30 min) to obtain negative electrode slurry; placing the prepared cathode slurry in a material groove of a photocuring 3D printer;
step three: guiding the designed phi 12mm multiplied by 2mm structural model into a printer;
step four: adjusting the levelness of the printing platform to ensure that the printing platform and the material groove are kept on the same plane and can be tightly attached;
step five: adjusting the height of the scraper to be 25 micrometers, so that the scraper can scrape the slurry to be flat until the thickness of the slurry layer is 25 micrometers, and setting the rotation period of the pre-exposure trough and the scraping period of the scraper to be 1 time;
step six: setting the slice thickness to be 25 micrometers, the single-layer exposure time to be 1-3s, and the single-layer exposure power to be 15-50mW/cm 2 ；
Step seven: starting a printer to print, taking down the blank after printing is finished, and cleaning to prepare a 3D printing zinc ion battery cathode material green blank, wherein the green blank is a circular sheet green blank with the thickness of 2mm and the diameter of 12 mm;
step eight: degumming the 3D printed zinc ion battery negative electrode material green blank at 400 ℃, and then performing densification sintering at 900 ℃ to obtain a zinc ion battery negative electrode material with certain mechanical strength;
step nine: carrying out partial reduction or complete reduction on the product obtained in the step by adopting thermal reduction or electrochemical reduction to obtain a three-dimensional porous negative electrode material containing zinc metal;
step ten: and assembling the zinc ion battery by using the reduced zinc ion battery cathode material.
Example 2
Preparing a zinc ion battery, comprising the following steps:
the method comprises the following steps: mixing 21g of zinc oxide powder (the diameter of the powder is 10-100 mu m), 9g of photosensitive resin 1, 6-hexanediol diacrylate (HDDA) and 0.27g of photoinitiator diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus (TPO) to obtain printing slurry;
step two: putting the mixed slurry into a planetary ball mill, and uniformly mixing (the rotating speed is 250rpm, and the time is 30 min) to obtain negative electrode slurry;
step three: put into DLP 3D with above-mentioned negative pole thick liquids and print in printing photocuring equipment: the slice thickness is 25 micrometers, the single-layer exposure time is 3s, and the single-layer exposure power is 20mW/cm 2 . The structural model is a three-cycle Minimal Surface (TPMS), and the size of a printed part is phi 12mm multiplied by 1mm;
step four: placing the printed green body into a muffle furnace, degumming under the air condition, heating from room temperature to 500 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1h, and cooling along with the furnace;
step five: and (3) carrying out densification sintering treatment on the degummed blank: under the protection of inert gas, heating from room temperature to 600 ℃ at a speed of 2 ℃/min, preserving heat for 1h, heating to 1000 ℃ at a speed of 1 ℃/min, preserving heat for 1h, and cooling along with the furnace;
step six: carrying out partial reduction or complete reduction on the blank in the above steps by adopting electrochemical reduction to obtain a three-dimensional zinc ion battery cathode material; performing electrochemical reduction on the sintered zinc oxide green body by using a three-electrode system in 6M potassium hydroxide solution at a voltage of-50 mV to obtain a three-dimensional zinc (zinc oxide) composite material electrode; as shown in fig. 2, the sintered zinc oxide blank and the 3D zinc anode material after electro-reduction are obtained; FIG. 3 shows the AC impedance spectra of the battery system during and before electrochemical reduction;
step seven: and assembling the zinc ion battery by using the reduced zinc ion battery cathode material.
Example 3
The procedure is substantially the same as in example 2, with the difference in the parameters of step four and step five:
step four: placing the printed green body into a muffle furnace, degumming under the air condition, heating from room temperature to 400 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 1h, and cooling along with the furnace;
step five: and (3) carrying out densification sintering treatment on the degummed blank: under the protection of inert gas, the temperature is raised from room temperature to 800 ℃ at the speed of 2 ℃/min, the temperature is maintained for 1h, then the temperature is raised to 1200 ℃ at the speed of 1 ℃/min, the temperature is maintained for 1h, and then furnace cooling is carried out.
The electrochemical performance of the electrode material was tested as follows:
(1) The test cell adopts a swagelok cell system, wherein the counter electrode is ammonium vanadate (NH) 4 V 4 O 10 ) Positive electrode, 2M ZnSO 4 The solution is electrolyte;
(2) The reversible capacity and the cycle performance of the electrode material are tested and analyzed by a constant-current charging and discharging method in the experiment. The working voltage range is 0.3-1.4V.
The three-dimensional zinc ion battery cathode prepared in example 2 is made into a working electrode according to the method, and corresponding electrochemical performance tests are performed, and the test result is shown in fig. 4, wherein the specific discharge capacity reaches 397mAh/g when charging and discharging are carried out at 0.1A/g.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a metal cathode of a zinc ion battery is characterized by comprising the following steps:
s1, forming the negative electrode slurry into a three-dimensional zinc ion battery negative electrode blank through photocuring 3D printing;
s2, sequentially degumming and densifying and sintering the three-dimensional zinc ion battery negative electrode blank;
and S3, reducing the sintered product to obtain a three-dimensional porous structure containing zinc metal, namely the zinc ion battery cathode.
2. The preparation method of the zinc ion battery cathode according to claim 1, wherein in the step S2, the three-dimensional zinc ion battery cathode blank is sequentially subjected to degumming, densification and sintering, and specifically comprises the following steps: carrying out gradient sintering on the three-dimensional zinc ion battery cathode blank under the air condition, wherein the temperature is 400-600 ℃, and fully pyrolyzing the photosensitive resin; then the blank body without the photosensitive resin is densified and sintered under the condition of inert gas, and the temperature is 900-1200 ℃.
3. The method for preparing the negative electrode of the zinc-ion battery according to claim 1, wherein the method for preparing the negative electrode slurry comprises the following steps: and uniformly mixing the negative active material powder with the photosensitive resin, the thickening agent and the photoinitiator to uniformly disperse the negative active material powder.
4. The method for preparing a negative electrode for a zinc-ion battery according to claim 3, wherein the negative electrode slurry comprises 30 to 90wt% of a negative electrode active material, 10 to 70wt% of a photosensitive resin, 0 to 20wt% of a thickener, and 0 to 3wt% of a photoinitiator.
5. The method for preparing the negative electrode of the zinc-ion battery according to claim 4, wherein the negative electrode active material is zinc oxide powder, the thickener is one or a mixture of several of polyurethane, polyacrylate, polyoxyethylene and cellulose thickeners, and the photosensitive resin is one or a mixture of several of acrylated epoxy resin, unsaturated polyester, polyurethane and polythiol/polyene photocurable resin.
6. The method for preparing a negative electrode for a zinc-ion battery according to claim 1, wherein the sintered product is partially or completely reduced by thermal reduction or electrochemical reduction in step S3.
7. The method for preparing the negative electrode of the zinc-ion battery according to any one of claims 1 to 6, wherein in the step S1, the photocuring 3D printing is a three-dimensional photocuring or digital light processing process.
8. A zinc ion battery negative electrode characterized by being prepared by the preparation method according to any one of claims 1 to 7.
9. A zinc ion battery comprising the zinc ion battery negative electrode of claim 8.
10. The zinc-ion battery of claim 9, further comprising a positive electrode material including nickel oxide, activated carbon, manganese oxide, vanadium oxide, prussian blue analog, organic compound, etc., and an electrolyte including potassium hydroxide solution, zinc sulfate solution, etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211214694.XA CN115513406A (en) | 2022-09-30 | 2022-09-30 | Zinc ion battery cathode, preparation method thereof and zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211214694.XA CN115513406A (en) | 2022-09-30 | 2022-09-30 | Zinc ion battery cathode, preparation method thereof and zinc ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115513406A true CN115513406A (en) | 2022-12-23 |
Family
ID=84507750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211214694.XA Pending CN115513406A (en) | 2022-09-30 | 2022-09-30 | Zinc ion battery cathode, preparation method thereof and zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115513406A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681129A (en) * | 2017-08-23 | 2018-02-09 | 北京航空航天大学 | A kind of zinc-base battery three-dimensional zinc/carbon composite and preparation method thereof |
| US20200156035A1 (en) * | 2018-09-21 | 2020-05-21 | California Institute Of Technology | 3d printing of metal containing structures |
| CN111993529A (en) * | 2020-08-24 | 2020-11-27 | 广东工业大学 | Light-cured metal forming method |
| CN112467083A (en) * | 2020-11-20 | 2021-03-09 | 南京理工大学 | Method for 3D printing of three-dimensional cathode |
| CN114103115A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of 3D printing battery electrode |
| CN114883669A (en) * | 2022-04-13 | 2022-08-09 | 西北工业大学 | Water system nickel-iron battery and preparation method thereof |
-
2022
- 2022-09-30 CN CN202211214694.XA patent/CN115513406A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681129A (en) * | 2017-08-23 | 2018-02-09 | 北京航空航天大学 | A kind of zinc-base battery three-dimensional zinc/carbon composite and preparation method thereof |
| US20200156035A1 (en) * | 2018-09-21 | 2020-05-21 | California Institute Of Technology | 3d printing of metal containing structures |
| CN111993529A (en) * | 2020-08-24 | 2020-11-27 | 广东工业大学 | Light-cured metal forming method |
| CN112467083A (en) * | 2020-11-20 | 2021-03-09 | 南京理工大学 | Method for 3D printing of three-dimensional cathode |
| CN114103115A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of 3D printing battery electrode |
| CN114883669A (en) * | 2022-04-13 | 2022-08-09 | 西北工业大学 | Water system nickel-iron battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ALEXIS MAUREL ET AL: "Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective", 《IEEE ACCESS》, vol. 9, 13 October 2021 (2021-10-13), pages 140656 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109103456B (en) | Preparation method of composite porous current collector for lithium metal negative electrode protection | |
| CN110010895A (en) | Carbon fiber loaded magnesium oxide particle crosslinking nano chip arrays composite material and preparation method and application | |
| CN110957477A (en) | Porous ceramic composite lithium metal cathode and preparation method thereof | |
| CN110890530A (en) | Lithium metal secondary battery based on porous ceramic composite lithium metal cathode and preparation method thereof | |
| CN116632254A (en) | Modified negative current collector and preparation method and application thereof | |
| CN113871724A (en) | Oxide solid electrolyte and preparation method and application thereof | |
| CN111705315B (en) | Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery | |
| CN115513406A (en) | Zinc ion battery cathode, preparation method thereof and zinc ion battery | |
| CN112921369B (en) | Lithium metal negative current collector surface thermal oxidation regulation and control method for prolonging cycle life | |
| CN115241412A (en) | Pole piece and battery | |
| CN115172639A (en) | Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof | |
| CN211017237U (en) | Porous ceramic composite lithium metal negative electrode and lithium metal secondary battery based on negative electrode | |
| CN114142033A (en) | Modified graphite negative electrode material for lithium ion battery | |
| CN113675376A (en) | Dendrite-free alkali metal ion battery based on solid/liquid phase conversion of negative electrode surface | |
| CN113224371A (en) | High-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery | |
| CN112164767B (en) | Silicon oxide-lithium composite material and preparation method and application thereof | |
| CN115000412B (en) | Preparation method and application of surface modified carbon cloth 3D framework | |
| CN113707845B (en) | Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery | |
| CN114221018B (en) | Preparation method of graphite felt lithium ion battery | |
| CN108346786A (en) | The preparation method and product of nano-silicon/carbon composite and nano silicon dioxide/carbon composite | |
| CN114975862B (en) | Secondary battery, electronic device and preparation method of secondary battery | |
| CN115036447B (en) | Lithium/sodium metal battery electrode plate protective coating and preparation method thereof | |
| CN113410451B (en) | Lithium metal negative electrode flexible protection material and preparation method thereof | |
| CN114242956B (en) | Polymer negative electrode protective layer and preparation method and application thereof | |
| CN115676888B (en) | Modified lithium tantalate modified graphene nanomaterial and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |