CN114551845A - Zinc ion battery with self-charging characteristic and preparation method thereof - Google Patents
Zinc ion battery with self-charging characteristic and preparation method thereof Download PDFInfo
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- CN114551845A CN114551845A CN202210195992.2A CN202210195992A CN114551845A CN 114551845 A CN114551845 A CN 114551845A CN 202210195992 A CN202210195992 A CN 202210195992A CN 114551845 A CN114551845 A CN 114551845A
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims abstract description 9
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- 239000007774 positive electrode material Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 43
- 229910021389 graphene Inorganic materials 0.000 abstract description 34
- 239000000758 substrate Substances 0.000 abstract description 25
- 229920000767 polyaniline Polymers 0.000 abstract description 14
- 239000008367 deionised water Substances 0.000 abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910002804 graphite Inorganic materials 0.000 abstract description 8
- 239000010439 graphite Substances 0.000 abstract description 8
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 239000012286 potassium permanganate Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000005588 protonation Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000004070 electrodeposition Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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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
- H01M4/362—Composites
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a zinc ion battery with self-charging characteristic and a preparation method thereof, wherein zinc trifluoromethanesulfonate is used as an electrolyte, is dissolved in deionized water, is adjusted to be acidic by sulfuric acid, is added with PVA, and is stirred for a certain time at a proper temperature to obtain gel electrolyte; the method comprises the steps of taking graphite paper treated by a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid as an active substrate, and further depositing polyaniline and metallic zinc on the active substrate to obtain a polyaniline/graphene oxide anode and a zinc/graphene oxide cathode. And forming the obtained positive electrode, negative electrode and gel electrolyte into the zinc ion battery with self-charging characteristic. The invention is based on an active graphene substrate, and utilizes the protonation principle of aniline to obtain the zinc ion battery which takes polyaniline as an active material and has self-charging characteristic. In the invention, the prepared zinc ion battery has good self-charging stability while meeting self-charging characteristics.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a zinc ion battery with self-charging characteristic and a preparation method thereof.
Background
With the development of science and technology, batteries have been applied to various fields such as automobiles, new energy sources, aerospace and the like, and the energy storage device has become an essential element in life. However, as an energy storage and supply device, after the electricity stored in the battery is used up, the battery is often charged by an external electric field to recover its efficiency. However, under the condition of no external electric field, the use of the battery is greatly limited, and the battery is only used as a disposable consumable, which is not in accordance with the current sustainable development concept. And zinc ion battery, different from the lithium ion battery that is common on the market, can rely on aqueous electrolyte as the electrolyte of battery and can assemble in the air, more green safety. Therefore, the preparation of the zinc ion battery which can carry out self-charging only by relying on the chemical reaction in the battery under the condition of no external electric field is very combined with the advancing direction of the current industry, and has great development potential.
Disclosure of Invention
This section is intended to summarize some aspects of the embodiments of the invention and to briefly introduce some of the more effective embodiments.
The present invention has been made keeping in mind the above problems occurring in the prior art.
In order to solve the above problems, the present invention provides the following technical solutions: a zinc ion battery with self-charging characteristics comprises a positive electrode, a negative electrode and a gel electrolyte; the positive electrode includes: polyaniline/graphene oxide; the negative electrode includes: metallic zinc/graphene oxide; the gel electrolyte includes: zinc trifluoromethanesulfonate, PVA, deionized water and sulfuric acid.
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the concentration of the aniline solution is 0.01-0.1 mol/L.
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the supporting electrolyte of the aniline solution can be sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid; the concentration of the acid is 0.1-1 mol/L.
As a preferable embodiment of the zinc ion battery having self-charging characteristics of the present invention, wherein: the current density range when depositing polyaniline is 0.1-0.2mA/cm2。
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the zinc salt of the metal zinc deposited on the negative electrode is zinc sulfate, and the concentration of the zinc sulfate is 0.1-0.2 mol/L.
As a preferable embodiment of the zinc ion battery having self-charging characteristics of the present invention, wherein: the current density range when depositing the metal zinc is (-80) - (-100) mA/cm2。
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the concentration of zinc trifluoromethanesulfonate in the gel electrolyte is 1-2 mol/L.
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the PH of the gel electrolyte is in the range of 2-4.
As a preferable aspect of the zinc ion battery having self-charging characteristics of the present invention, wherein: the mass ratio of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid is 1: 40: 4.
another object of the present invention is to provide a method for preparing a zinc ion battery having a self-charging characteristic as described in any of the above, comprising:
cutting graphite paper, immersing the paper in a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid, inserting the paper in the mixed solution for a period of time, taking out the paper, and washing the paper with deionized water to obtain an active graphene oxide substrate, wherein as shown in figure 1, a plurality of graphene oxides are loaded on the surface of the graphite treated by the mixed solution, so that the specific surface area of the graphite is increased, a large number of active sites are provided for the deposition of polyaniline, and the protonation effect of the polyaniline is promoted;
respectively polymerizing aniline on an active graphene oxide substrate by using an electrochemical deposition method to obtain a battery anode, and depositing metal zinc on the active graphene oxide substrate to obtain a battery cathode;
adding zinc trifluoromethanesulfonate into deionized water for dissolving, adjusting the pH value with sulfuric acid, adding PVA, heating while rapidly stirring to obtain transparent viscous liquid, and cooling to obtain transparent gel electrolyte.
The positive electrode and the negative electrode obtained above are assembled together with a gel electrolyte to form a zinc ion battery having self-charging characteristics.
The invention has the beneficial effects that:
compared with the prior art, the invention has the following beneficial effects: according to the invention, based on the active graphene oxide substrate, active polyaniline and metal zinc are deposited on the substrate, and a solid electrolyte is combined to obtain the zinc ion battery with self-charging characteristic, and the method is simple and can be commercialized.
Description of the drawings:
in order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an SEM image of an activated graphene oxide substrate used in the present invention;
fig. 2 is a graph of open circuit voltage versus cycle number for 15 minutes of air exposure for a zinc ion battery assembled in example 1 of the present invention;
fig. 3 is a graph of open circuit voltage versus cycle number for 15 minutes of air exposure for a zinc ion battery assembled in example 2 of the present invention;
fig. 4 is a graph of open circuit voltage versus cycle number for 15 minutes of air exposure for a zinc ion battery assembled in example 3 of the present invention;
fig. 5 is a graph of open circuit voltage-cycle number for 15 minutes of exposure to air for the assembled zinc-ion cell of comparative example 1 of the present invention.
The specific implementation mode is as follows:
in order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments of the present invention are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
(1) preparing an active graphene oxide substrate: immersing 1 x 30mm graphite strips into a graphite material with a mass ratio of 1: 40: 4, reacting for 10s in a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid of about 1mm, and washing with deionized water to obtain an active graphene oxide substrate;
(2) preparing a gel electrolyte: adding 7.27g of zinc trifluoromethanesulfonate into 10ml of deionized water, adjusting the pH value to 2 with sulfuric acid after complete dissolution, adding 1g of PVA, heating to 85 ℃, simultaneously accelerating stirring for 2h to obtain a transparent viscous solution, standing and cooling to obtain a gel electrolyte;
(3) preparing a positive electrode: adding 10ul aniline into 100ml 1M sulfuric acid solution to obtain aniline solution, soaking active graphene oxide substrate into the obtained aniline solution to serve as a working electrode, and using a platinum sheet as a counter electrode, wherein two electrode systems are used and are 0.2mA/cm2Carrying out electrodeposition for 3 hours under current density to obtain a polyaniline/graphene oxide composite electrode, namely a positive electrode;
(4) preparing a negative electrode: immersing the active graphene oxide substrate in 0.2M zinc sulfate solution, using a platinum sheet as a counter electrode and KCl as a reference electrode, and using-80 mA/cm under a three-electrode system2Constant current electrodeposition of 20min, obtaining a metal zinc/graphene oxide composite electrode, namely a negative electrode;
(5) assembling the battery: the zinc ion battery with self-charging characteristic is formed by the sequence of a positive electrode, a gel electrolyte and a negative electrode.
Fig. 2 is a graph of open circuit voltage of the assembled zinc-ion battery of example 1 in air for 15 minutes versus the number of cycles, when the battery is discharged to a low voltage of 0.5V, polyaniline on the positive electrode of the battery reacts with oxygen in the air due to the protonation effect of polyaniline, and the open circuit voltage of the battery increases rapidly, within 15 minutes, the open circuit voltage can reach 0.8383V, and after 50 cycles, the self-charging stability is maintained at 94.04%, which indicates that the self-charging performance of the battery can be reused and the loss is small.
Example 2:
(1) preparing an active graphene oxide substrate: immersing 1 x 30mm graphite strips into a graphite material with a mass ratio of 1: 40: 4, reacting for 10s in a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid of about 1mm, and washing with deionized water to obtain an active graphene oxide substrate;
(2) preparing a gel electrolyte: adding 7.27g of zinc trifluoromethanesulfonate into 10ml of deionized water, adjusting the pH value to 2 with sulfuric acid after complete dissolution, adding 1g of PVA, heating to 85 ℃, simultaneously accelerating stirring for 2h to obtain a transparent viscous solution, standing and cooling to obtain a gel electrolyte;
(3) preparing a positive electrode: adding 20ul aniline into 100ml 1M hydrochloric acid solution to obtain aniline solution, soaking active graphene oxide substrate into the obtained aniline solution as working electrode, and using two electrode systems of 0.15 mA/cm as counter electrode2Carrying out electrodeposition for 3 hours under current density to obtain a polyaniline/graphene oxide composite electrode, namely a positive electrode;
(4) preparing a negative electrode: immersing the active graphene oxide substrate in 0.2M zinc sulfate solution, using a platinum sheet as a counter electrode and KCl as a reference electrode, and using-90 mA/cm under a three-electrode system2Performing constant current electrodeposition for 20min to obtain a metal zinc/graphene oxide composite electrode, namely a negative electrode;
(5) assembling the battery: the zinc ion battery with self-charging characteristic is formed by the sequence of a positive electrode, a gel electrolyte and a negative electrode.
Fig. 2 is a graph of open circuit voltage of the assembled zinc-ion battery of example 2 in air for 15 minutes versus cycle number, with the open circuit voltage for the first self-charge for 15 minutes being 0.8491 and the self-charge stability remaining at 94.05% after 50 cycles.
Example 3:
(1) preparing an active graphene oxide substrate: immersing 1 x 30mm graphite strips into a graphite material with a mass ratio of 1: 40: 4, reacting for 10s in a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid of about 1mm, and washing with deionized water to obtain an active graphene oxide substrate;
(2) preparing a gel electrolyte: adding 7.27g of zinc trifluoromethanesulfonate into 10ml of deionized water, adjusting the pH value to 2 with sulfuric acid after complete dissolution, adding 1g of PVA, heating to 85 ℃, simultaneously accelerating stirring for 2h to obtain a transparent viscous solution, standing and cooling to obtain a gel electrolyte;
(3) preparing a positive electrode: obtaining aniline solution from 10ul aniline 100ml 1M phosphoric acid solution, immersing active graphene oxide substrate into the obtained aniline solution as a working electrode, using a platinum sheet as a counter electrode, and using two electrode systems of 0.2mA/cm2Carrying out electrodeposition for 3 hours under current density to obtain a polyaniline/graphene oxide composite electrode, namely a positive electrode;
(4) preparing a negative electrode: immersing the active graphene oxide substrate in 0.2M zinc sulfate solution, using a platinum sheet as a counter electrode and KCl as a reference electrode, and using-100 mA/cm under a three-electrode system2Performing constant current electrodeposition for 20min to obtain a metal zinc/graphene oxide composite electrode, namely a negative electrode;
(5) assembling the battery: the zinc ion battery with self-charging characteristic is formed by the sequence of a positive electrode, a gel electrolyte and a negative electrode.
Fig. 3 is a graph of open circuit voltage of the assembled zinc-ion battery of example 3 in air for 15 minutes versus cycle number, with the open circuit voltage for the first self-charge for 15 minutes being 0.8544 and the self-charge stability after 50 cycles remaining at 91.76%.
Comparative example 1:
(1) preparing an active graphene oxide substrate: immersing 1 x 30mm graphite strips into a graphite material with a mass ratio of 1: 40: 4, reacting for 10s in a mixed solution of potassium permanganate, concentrated sulfuric acid and concentrated phosphoric acid of about 1mm, and washing with deionized water to obtain an active graphene oxide substrate;
(2) preparing a gel electrolyte: adding 3.64g of zinc trifluoromethanesulfonate into 10ml of deionized water, adjusting the pH value without adding sulfuric acid after completely dissolving, directly adding 1g of PVA when the pH value of the solution is between 5 and 6, heating to 85 ℃, simultaneously accelerating stirring for 2 hours to obtain a transparent viscous solution, and standing and cooling to obtain a gel electrolyte;
(3) preparing a positive electrode: adding 10ul aniline into 30ml 1M sulfuric acid solution to obtain aniline solution, soaking active graphene oxide substrate into the obtained aniline solution to serve as a working electrode, and using a platinum sheet as a counter electrode, wherein two electrode systems are used and are 0.2mA/cm2Carrying out electrodeposition for 3 hours under current density to obtain a polyaniline/graphene oxide composite electrode, namely a positive electrode;
(4) preparing a negative electrode: immersing the active graphene oxide substrate in 0.2M zinc sulfate solution, using a platinum sheet as a counter electrode and KCl as a reference electrode, and using-100 mA/cm under a three-electrode system2Performing constant current electrodeposition for 20min to obtain a metal zinc/graphene oxide composite electrode, namely a negative electrode;
(5) assembling the battery: the zinc ion battery with self-charging characteristic is formed by the sequence of a positive electrode, a gel electrolyte and a negative electrode.
Fig. 4 is a graph of open circuit voltage at 15 minutes versus cycle number for the assembled zinc-ion cell of comparative example 1 in air, with an open circuit voltage of 0.8414 for the first self-charge at 15 minutes and a self-charge stability of only 86.04% after 50 cycles.
Comparative example 1 shows that the protonation degree of aniline is higher in an acidic environment, and the reversibility of the self-charging process of the zinc ion battery is improved, so that the self-charging stability of the zinc ion battery is further improved.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A zinc-ion battery having self-charging characteristics, characterized by: comprises a positive electrode, a negative electrode and a gel electrolyte; the gel electrolyte comprises zinc salt solution, PVA and sulfuric acid.
2. The zinc-ion battery having self-charging characteristics according to claim 1, wherein: the zinc salt is zinc trifluoromethanesulfonate, and the concentration of the zinc salt solution is 1-2 mol/L.
3. The zinc-ion battery having self-charging characteristics according to claim 2, wherein: the mass range of PVA used was 0.5-1 g.
4. The zinc-ion battery having self-charging characteristics according to claim 2, wherein: the pH value of the gel electrolyte is in the range of 2-4.
5. The zinc-ion battery having self-charging characteristics according to claim 1, wherein: the concentration range of the positive active material aniline solution is 0.01-0.1 mol/L.
6. The zinc-ion battery having self-charging characteristics according to claim 5, wherein: the supporting electrolyte in the aniline solution is sulfuric acid, phosphoric acid, hydrochloric acid or perchloric acid.
7. The zinc-ion battery having self-charging characteristics according to claim 6, wherein: the concentration of the supporting electrolyte ranges from 0.1 to 1 mol/L.
8. The zinc-ion battery having self-charging characteristics according to claim 6, wherein: the current density ranges for aniline deposition were: 0.1-0.2mA/cm-2。
9. The zinc ion battery having self-charging characteristics as claimed in claim 1, wherein the zinc salt used for depositing the metallic zinc of the negative electrode is a zinc sulfate solution having a concentration of 0.1 to 0.2 mol/L.
10. The zinc-ion battery of claim 7, wherein said zinc metal is deposited at a current density of (-80) - (-100) mA/cm2。
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| Publication number | Priority date | Publication date | Assignee | Title |
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