CN117293412A - Water-based zinc ion battery containing negative electrode protection film and zinc negative electrode for battery - Google Patents
Water-based zinc ion battery containing negative electrode protection film and zinc negative electrode for battery Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 107
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 96
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 46
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 46
- 239000000661 sodium alginate Substances 0.000 claims abstract description 46
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000017 hydrogel Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- -1 sodium alginate modified zinc Chemical class 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 9
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 150000001450 anions Chemical class 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 7
- 229960001763 zinc sulfate Drugs 0.000 description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 description 7
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
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 water-based zinc ion batteries, and particularly relates to a water-based zinc ion battery containing a negative electrode film and a zinc negative electrode for the battery. The invention solves the defects of the existing water system zinc ion battery, utilizes sodium alginate to form anion hydrogel on the surface of a zinc sheet, achieves the effects of adsorbing zinc ions and rejecting anions, and realizes the inhibition of zinc dendrite growth and interface side reaction.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries, and particularly relates to a water-based zinc ion battery containing a negative electrode film and a zinc negative electrode for the battery.
Background
Lithium ion batteries are widely used in the field of electric vehicles and portable electronic devices as well-developed electrochemical energy storage systems. However, the problems of high production cost, high safety and the like exist, so that the application of large-scale electrochemical energy storage cannot be satisfied. Rechargeable batteries based on other polyvalent metals are therefore widely studied. Among these, zinc metal has many advantages as a battery anode over other metals (e.g., lithium, sodium, potassium, magnesium, and aluminum), such as: the resource abundance, low production cost, higher hydrogen evolution overpotential and energy density; aqueous zinc ion cells are therefore considered to be a good choice for achieving large-scale electrochemical energy storage. However, the water-based zinc ion battery has the problems of dendrite growth, corrosion, passivation and the like of the negative electrode in the current practical research; these problems ultimately lead to batteries with lower cycle performance and rate capability, which can affect their commercial applications.
The problems existing in the zinc anode can be solved at present by methods such as electrolyte optimization and anode surface modification. The electrolyte is optimized by mainly adding a polar organic polymer additive into the electrolyte, so that the polar organic polymer additive is adsorbed on the surface of the tip metal under the action of an electrostatic field, and the growth of negative dendrite is inhibited by an electrostatic shielding effect, thereby prolonging the service life of the battery. The zinc cathode surface modification is mainly realized by establishing a buffer layer to isolate the direct contact between the cathode surface and electrolyte, so that the uniform deposition of zinc ions is promoted, and the cycle performance of the battery is improved. The zinc anode surface modification is more suitable for inhibiting corrosion, passivation and other problems of the anode because the use of the electrolyte additive generally has the problems of higher cost, low potential safety hazard, difficult recovery and treatment and the like.
Buffer layers as zinc anode surface modifications can be divided into three types: organic polymer coatings, inorganic metal salt coatings, and metal alloying coatings. The national institute of science, qingdao bioenergy and process institute Cui Guanglei (Energy environment. Sci.2019,12,1938) has reported organic polyamide coatings, where hydrogen bonds on the polymer can bind zinc ions and allow uniform deposition on the negative electrode by limiting irregular diffusion during zinc ion deposition. The research on layered nano eutectic zinc-aluminum alloy by the university of Jilin group Lang Xingyou (Nat. Commun.2020,11,1634) shows that the electrostatic shielding effect generated by the alloy structure can effectively inhibit the growth of zinc dendrites. Although a series of negative electrode surface modification researches have achieved a certain result in inhibiting zinc negative electrode corrosion and other problems, the preparation process and cost of the coating cannot be used for large-scale energy storage application, and meanwhile, the overall performance of the battery is affected to a certain extent by the impedance and polarization of the coating diaphragm, so that the preparation of the negative electrode surface coating which is efficient and beneficial to large-scale production is still one of the main problems of the current researches.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the water-based zinc ion battery containing the negative electrode protection film, which solves the defects of the existing water-based zinc ion battery, and utilizes sodium alginate to form anionic hydrogel on the surface of a zinc sheet so as to achieve the effects of adsorbing zinc ions and repelling anions and inhibit the growth of zinc dendrites and the occurrence of interface side reactions.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a water-based zinc ion battery containing a negative electrode protection film uses sodium alginate modified zinc sheets as a zinc negative electrode.
Further, the separator of the water-based zinc ion battery is glass fiber.
The electrolyte of the water-based zinc ion battery contains an aqueous solution of zinc ions.
In the sodium alginate modified zinc sheet, sodium alginate is used as an anionic hydrogel film to be fixed on the surface of the zinc sheet, and the preparation method of the sodium alginate modified zinc sheet comprises the following steps:
step 1, dissolving sodium alginate in deionized water, and fully stirring to obtain sodium alginate aqueous solution;
and 2, spin-coating the sodium alginate aqueous solution on the surface of the zinc foil, and curing to obtain the sodium alginate modified zinc sheet.
In the step 1, the mass concentration of the sodium alginate is 300-350mg/mL.
In the step 2, the zinc foil adopts a zinc foil wafer with the diameter of 16mm and the thickness of 35-100 mu m.
In the step 2, the volume of the solution level of the sodium alginate which is spin-coated is 50-100 mu L/cm 2 。
In the step 2, the spin coating speed is 3500rpm and the time is 10s.
In the step 2, the curing is performed by UV curing or oven drying, preferably UV curing, and the UV curing time is 10-15min. The temperature of the drying and curing is 40-70 ℃ and the time is 2-5h.
According to the technical scheme, sodium alginate is coated on the surface of a zinc sheet to form anionic hydrogel, so that the interface reaction between a zinc negative electrode and electrolyte can be regulated, zinc ions are adsorbed to be uniformly deposited or dissolved on the surface of the negative electrode, thereby inhibiting the growth of zinc dendrites, rejecting anions in the electrolyte, and inhibiting side reactions at the interface, so that the problems of corrosion and passivation of a battery and the like are relieved.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the defects of the existing water system zinc ion battery, utilizes sodium alginate to form anion hydrogel on the surface of a zinc sheet, achieves the effects of adsorbing zinc ions and rejecting anions, and realizes the inhibition of zinc dendrite growth and interface side reaction.
2. The polysaccharide structure of the sodium alginate adopted by the invention contains a large number of free carboxyl and hydroxyl, can promote the sodium alginate to adsorb zinc ions and form a complex type protection structure, and the material is low in cost, green and pollution-free.
3. The invention forms the negative ion type hydrogel protective layer on the surface of the zinc sheet in an in-situ growth mode, thereby effectively inhibiting the problems of dendrite growth, corrosion, passivation and the like of the zinc cathode.
Drawings
FIG. 1 is a graph showing that the symmetric cell of the modified metallic zinc prepared according to example 1 was at 5mA/cm 2 And 2.5mAh/cm 2 Long cycle performance at current density of (2);
FIG. 2 is a graph of symmetric cells at 5mA/cm for modified metallic zinc prepared according to example 2 2 And 2.5mAh/cm 2 Long cycle performance at current density of (2);
FIG. 3 is a graph showing that the symmetric cell of the modified metallic zinc prepared according to example 3 was at 5mA/cm 2 And 2.5mAh/cm 2 Long cycle performance at current density of (2);
FIG. 4 is a surface SEM image of modified metallic zinc prepared according to example 1 and unmodified metallic zinc of comparative example 1
FIG. 5 is a contact angle of modified metallic zinc prepared according to example 1 with unmodified metallic zinc in 3M aqueous zinc sulfate solution of comparative example 1, wherein Bare Zn represents unmodified metallic zinc and SA coated Zn represents metallic zinc modified by sodium alginate hydrogel film;
FIG. 6 is a Taphil plot of a symmetrical cell of modified metallic zinc prepared according to example 1 and a symmetrical cell of unmodified metallic zinc of comparative example 1, wherein Bare Zn represents unmodified metallic zinc and SA coated Zn represents metallic zinc modified by a sodium alginate hydrogel film;
FIG. 7 is a 0.5mA/cm symmetrical cell of modified metallic zinc prepared according to example 1 and a symmetrical cell of unmodified metallic zinc of comparative example 1 2 And 0.5mAh/cm 2 Wherein BareZn represents unmodified metallic zinc and SA coated Zn represents sodium alginate hydrogel film modified metallic zinc;
FIG. 8 shows that the whole cell of modified metallic zinc prepared according to example 1 and the whole cell of unmodified metallic zinc of comparative example 1 were at 5 A.times.g -1 Wherein Bare Zn represents unmodified metallic zinc and SA coated Zn represents sodium alginate hydrogel film modified metallic zinc;
FIG. 9 shows the 0.5mA/cm symmetrical cell of the modified metallic zinc prepared according to example 1 and the asymmetrical cell of the unmodified metallic zinc of comparative example 1 2 And 0.5mAh/cm 2 Surface SEM images after 50 cycles of current density, wherein Bare Zn represents unmodified metallic zinc and SA coated Zn represents sodium alginate hydrogel film modified metallic zinc;
FIG. 10 shows a 0.5mA/cm symmetrical cell of modified metallic zinc prepared according to example 1 and a symmetrical cell of unmodified metallic zinc of comparative example 1 2 And 0.5mAh/cm 2 XRD pattern after 15 cycles at current density of (c) wherein Bare Zn represents unmodified metallic zinc and SA coated Zn represents sodium alginate hydrogel film modified metallic zinc.
Detailed Description
Specific embodiments of the present invention will be described in detail with reference to fig. 1 to 10, but do not limit the claims of the present invention.
Example 1
Commercial zinc metal discs of diameter 16mm and thickness about 75 μm were sanded to remove surface oxides and washed with ethanol and subsequently dried for use. 300mg of sodium alginate was dissolved in 1mL of deionized water, and stirred to obtain an aqueous sodium alginate solution. 150mL of sodium alginate aqueous solution is spin-coated on the surface of the treated zinc sheet by using a spin coater, the rotating speed is 3500rpm, and the time is 10s. And (3) curing the spin-coated zinc sheet by using a UV curing lamp for 10-15min to obtain the modified metal zinc sheet. The modified metal zinc sheet is used as an anode and a cathode, glass fiber is used as a diaphragm, and 3M zinc sulfate aqueous solution is used as electrolyte to assemble the CR2032 symmetrical battery; and beta-MnO is added 2 As a positive electrode, a modified metallic zinc sheet was used as a negative electrode, a glass fiber was used as a separator, and a mixed aqueous solution of 3M zinc sulfate and 0.2M manganese sulfate was used as an electrolyte, and a CR2032 type full cell was assembled.
Example 2
Commercial zinc metal discs of diameter 16mm and thickness about 75 μm were sanded to remove surface oxides and washed with ethanol and subsequently dried for use. 300mg of sodium alginate was dissolved in 1mL of deionized water, and stirred to obtain an aqueous sodium alginate solution. 100mL of sodium alginate aqueous solution is spin-coated on the surface of the treated zinc sheet by using a spin coater, the rotating speed is 3500rpm, and the time is 10s. And (3) curing the spin-coated zinc sheet by using a UV curing lamp for 10-15min to obtain the modified metal zinc sheet. And (3) using the modified metal zinc sheet as an anode and a cathode, using glass fiber as a diaphragm, and using a 3M zinc sulfate aqueous solution as an electrolyte to assemble the CR2032 type symmetrical battery.
Example 3
Commercial zinc metal discs of diameter 16mm and thickness about 75 μm were sanded to remove surface oxides and washed with ethanol and subsequently dried for use. 300mg of sodium alginate was dissolved in 1mL of deionized water, and stirred to obtain an aqueous sodium alginate solution. 200mL of sodium alginate aqueous solution is spin-coated on the surface of the treated zinc sheet by using a spin coater, the rotating speed is 3500rpm, and the time is 10s. And (3) curing the spin-coated zinc sheet by using a UV curing lamp for 10-15min to obtain the modified metal zinc sheet. And (3) using the modified metal zinc sheet as an anode and a cathode, using glass fiber as a diaphragm, and using a 3M zinc sulfate aqueous solution as an electrolyte to assemble the CR2032 type symmetrical battery.
Comparative example 1
Commercial zinc metal discs of diameter 16mm and thickness about 75 μm were sanded to remove surface oxides and washed with ethanol and subsequently dried for use. Taking the dried metal zinc sheet as an anode and a cathode, taking glass fiber as a diaphragm, and taking a 3M zinc sulfate aqueous solution as an electrolyte to assemble a CR2032 type symmetrical battery; and beta-MnO is added 2 As a positive electrode, a dried metallic zinc sheet was used as a negative electrode, a glass fiber was used as a separator, and a mixed aqueous solution of 3M zinc sulfate and 0.2M manganese sulfate was used as an electrolyte, and a CR2032 type full cell was assembled.
As can be seen from fig. 1 to fig. 3, the film prepared from 150mL of sodium alginate aqueous solution in example 1 has better effect of protecting zinc cathode; the symmetrical battery assembled in example 1 has a smaller overpotential and a longer cycle life during cycling, and can stably operate for approximately 60 hours at a cyclic overpotential of about 0.8V, relative to the symmetrical batteries assembled in examples 2 and 3.
As can be seen from the SEM image of fig. 4, the modified metallic zinc surface obtained in example 1 is smoother and smoother than the unmodified metallic zinc surface in comparative example 1, which is more advantageous for uniform diffusion of zinc ions at the negative electrode and reduced tip effect.
As can be seen from the contact angle test of fig. 5, the modified metallic zinc obtained by example 1 has a surface that is more hydrophilic than the unmodified metallic zinc, facilitating the deposition or dissolution of zinc ions on the surface of the negative electrode during cycling of the battery.
As can be seen from the tafel plot of the symmetrical cell of fig. 6, the modified metallic zinc prepared in example 1 has a higher corrosion voltage and lower corrosion current than the unmodified metallic zinc of comparative example 1, indicating that the modified metallic zinc has a higher corrosion resistance relative to commercial zinc sheets.
As can be seen from the view of figure 7,the symmetrical battery prepared by example 1 had better cycling stability than the non-modified symmetrical battery of comparative example 1, and the battery was at 0.5mA/cm 2 And 0.5mAh/cm 2 Stable operation under the condition is more than 900 hours.
As can be seen from FIG. 8, in the case of beta-MnO 2 In a full cell system which is a positive electrode material, the full cell modified in example 1 also exhibits superior cycle performance and rate performance to those of the full cell unmodified in comparative example 1, and the cell can be at 5A×g -1 Is stable for 2000 cycles while maintaining a high specific capacity (132.2 mAh/g).
As can be seen from fig. 9, the surface of the modified zinc metal prepared in example 1 is still a smooth surface after 50 cycles, so that the crosslinked network structure formed by the sodium alginate film can be clearly observed, in contrast to the surface of the unmodified zinc metal of comparative example 1, which is very rough, the accumulation of byproducts on the surface can be observed.
As can be seen from the XRD results of fig. 10, after 15 cycles of discharge, no by-product was generated on the modified zinc surface, but zinc sulfate hydroxide was generated on the unmodified zinc sheet surface as a by-product.
According to comparison of the embodiment and the comparative example, the sodium alginate film can effectively prevent the growth of dendrites of the zinc cathode, inhibit corrosion and passivation of the zinc cathode in the circulation process, and effectively improve the circulation performance and the multiplying power performance of the battery; namely, the zinc sheet modified by the sodium alginate anion film can effectively regulate the interface reaction between the zinc cathode and the electrolyte, adsorb zinc ions to enable the zinc ions to be uniformly deposited or dissolved on the surface of the cathode, repel anions in the electrolyte, inhibit side reactions at the interface, and further alleviate the problems of corrosion, passivation and the like of the battery.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (10)
1. The water-based zinc ion battery containing the negative electrode protection film is characterized in that: sodium alginate modified zinc sheet is used as zinc cathode.
2. The aqueous zinc ion battery containing a negative electrode protective film according to claim 1, wherein: the separator of the water-based zinc ion battery is made of glass fiber.
3. The aqueous zinc ion battery containing a negative electrode protective film according to claim 1, wherein: the electrolyte of the water-based zinc ion battery contains an aqueous solution of zinc ions.
4. A zinc anode containing an anode protective film for a water-based zinc ion battery, characterized by: the zinc cathode adopts sodium alginate modified zinc sheets.
5. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 4, wherein: in the sodium alginate modified zinc sheet, sodium alginate is used as an anionic hydrogel film to be fixed on the surface of the zinc sheet.
6. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 5, wherein: the preparation method of the sodium alginate modified zinc sheet comprises the following steps:
step 1, dissolving sodium alginate in deionized water, and fully stirring to obtain sodium alginate aqueous solution;
and 2, spin-coating the sodium alginate aqueous solution on the surface of the zinc foil, and curing to obtain the sodium alginate modified zinc sheet.
7. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 6, wherein: in the step 1, the mass concentration of the sodium alginate is 300-350mg/mL.
8. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 6, wherein: in the step 2, the zinc foil adopts a zinc foil wafer with the diameter of 16mm and the thickness of 35-100 mu m.
9. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 6, wherein: in the step 2, the volume of the solution level of the sodium alginate which is spin-coated is 50-100 mu L/cm 2 。
10. The zinc anode comprising an anode protective film for an aqueous zinc-ion battery according to claim 6, wherein: in the step 2, the spin coating speed is 3500rpm and the time is 10s.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210456462.9A CN117293412A (en) | 2022-04-28 | 2022-04-28 | Water-based zinc ion battery containing negative electrode protection film and zinc negative electrode for battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210456462.9A CN117293412A (en) | 2022-04-28 | 2022-04-28 | Water-based zinc ion battery containing negative electrode protection film and zinc negative electrode for battery |
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| CN117293412A true CN117293412A (en) | 2023-12-26 |
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