CN111446508B - High-concentration solution and application and preparation method thereof - Google Patents
High-concentration solution and application and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 17
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 239000011592 zinc chloride Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 229940006460 bromide ion Drugs 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- DDFGPANTDSVNPE-UHFFFAOYSA-L zinc;dibromide;hydrate Chemical compound O.[Zn+2].[Br-].[Br-] DDFGPANTDSVNPE-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004246 zinc acetate Substances 0.000 abstract description 14
- 238000009830 intercalation Methods 0.000 abstract description 13
- 230000002687 intercalation Effects 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052794 bromium Inorganic materials 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 229940102001 zinc bromide Drugs 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 235000005074 zinc chloride Nutrition 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 229910021389 graphene Inorganic materials 0.000 description 13
- 238000007599 discharging Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- -1 specifically Chemical compound 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- LEQISTNVGGEONS-UHFFFAOYSA-L dizinc bromide chloride Chemical compound [Br-].[Zn+2].[Cl-].[Zn+2] LEQISTNVGGEONS-UHFFFAOYSA-L 0.000 description 2
- AKJCEQXPPZJWES-UHFFFAOYSA-J dizinc tetrabromide Chemical compound [Zn+2].[Zn+2].[Br-].[Br-].[Br-].[Br-] AKJCEQXPPZJWES-UHFFFAOYSA-J 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940060038 chlorine Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WLBHJIHRLZNSIV-UHFFFAOYSA-J dizinc tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Zn+2].[Zn+2] WLBHJIHRLZNSIV-UHFFFAOYSA-J 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011787 zinc oxide 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention provides a high-concentration solution which is suitable for electrolyte, at least zinc ions, bromide ions and chloride ions are contained in the solution, and a new 'dissolved salt' is formed through the 'multi-salt co-dissolution' effectMixture ", greatly increasing the concentration of the solution. Furthermore, the invention also provides an ultrahigh-concentration solution, which also contains zinc acetate, and the zinc acetate can not continue to aggregate and grow through the end-capping effect of the zinc acetate, so that the zinc acetate becomes inorganic oligomers with larger molecular weight and stably exists in the solution, and the concentration of the inorganic oligomers can even reach 45mol kg‑1. The high-concentration electrolyte not only effectively inhibits the electrolysis of water, but also reduces the oxidation potential of bromide ions, further promotes the intercalation of bromine in the battery anode material, and greatly improves the specific capacity (about 638mAh g) of the anode‑1). And the increase of the concentration of active ions of the electrolyte can reduce the using amount of the electrolyte, thereby being beneficial to the improvement of the energy density of the non-rocking chair type battery.
Description
Technical Field
The invention relates to a high-concentration solution and application thereof in a water-based dual-ion battery, wherein the concentration of the solution can reach 30mol kg-1As described above, the specific capacity of the battery can be greatly improved.
Background
Due to the rapid development of renewable energy technologies in recent years, the grid-level energy storage demand is increasing. Although lithium ion batteries dominate the electrochemical energy storage market including portable electronic devices and electric vehicles by virtue of their high energy density, their natural abundance and uneven distribution of natural lithium resources make it unreasonable to use them for power grid energy storage in the gigawatt level and also cause high cost problems. The water system electrochemical energy storage device is low in price and extremely high in safety, and provides a solution for large-scale storage of renewable energy.
However, the energy density of the current lithium-free battery is generally far lower than that of the lithium ion battery, and the phenomenon is particularly obvious in an aqueous system. While the use of "water-in-salt" type electrolytes is effective in increasing the energy density of aqueous electrochemical energy storage devices, most of these electrolytes are based on expensive organic lithium salts. The technology of preparing an aqueous electrolyte with ultrahigh concentration by using non-lithium elements with high natural abundance and developing a lithium-free aqueous rechargeable battery with low cost and high energy density is a problem to be solved urgently, but also faces huge challenges.
Disclosure of Invention
An object of the present invention is to provide a highly concentrated aqueous solution suitable for use in an electrolyte, the solution having at least zinc ions, bromide ions and chloride ions, wherein the concentration of zinc ions is 30mol kg-1The above. Specifically, the solution at least comprises two solutes of zinc chloride and zinc bromide, zinc bromide and chlorine dissolved in waterThe solution composed of zinc oxide greatly increases the concentration of the solution by 'multi-salt co-dissolution', namely, a high-concentration salt solution is used as a new solvent to dissolve another unhydrated salt and form a new 'dissolved salt mixture', wherein the concentration of zinc ions can reach 30mol kg-1Above, concentration mol kg-1Refers to the amount of solute dissolved per kilogram of water.
In the solution, the zinc bromide and the zinc chloride can be mixed at any ratio, and the concentration range of bromide ions is 15-90 mol kg in general-1The concentration range of the chloride ions is 15-90 mol kg-1. In certain embodiments, the ratio of the concentrations of bromide ion to chloride ion is 1:3, the concentration of zinc ions in the binary system solution can be effectively improved.
Another objective of the present invention is to provide an ultra-high concentration solution, which further contains acetate ions, specifically, zinc acetate as a solute, and further prevents the salt from continuing to aggregate and grow by the "capping" effect of zinc acetate, so that inorganic oligomers with large molecular weight stably exist in the solution. The concentration of zinc ions is 50mol kg to maintain the liquid phase state-1The concentration of acetic acid high ion is 10mol kg-1The following.
Experiments prove that the concentration ratio of bromide ions to chloride ions is 1:3, the concentration of zinc ions in the three-system solution can be effectively improved.
The invention also aims to provide the application of the solution in the electrolyte of the battery, the electrolyte with high concentration not only effectively inhibits the electrolysis of water, but also reduces the oxidation potential of bromide ions, promotes the intercalation of bromine in the anode material of the battery, and greatly improves the specific capacity of the anode (about 638mAh g)-1). And the increase of the concentration of active ions of the electrolyte can reduce the using amount of the electrolyte, thereby being beneficial to the improvement of the energy density of the non-rocking chair type battery.
Another object of the present invention is to provide an application of the above solution in battery electrolyte, wherein the high concentration electrolyte realizes breakthrough of bromine I-stage intercalation from the existing single-layer graphene to the macroscopic material (in the prior art, bromine I-stage intercalation is observed only on the single-layer graphene, and only the bromine I-stage intercalation can be realized in the macroscopic graphite material, but the single-layer graphene cannot be used industrially), and the battery anode has high specific capacity.
In certain embodiments, the positive electrode of the battery employs carbon materials, particularly carbon nanotubes, natural graphite, expanded graphite, graphene assemblies, and other carbon materials having a graphite lattice structure. The examples demonstrate that stage I intercalation of bromide ions can be achieved regardless of the cathode material.
In certain embodiments, the negative electrode of the battery employs a zinc negative electrode comprising metallic zinc, zinc-containing alloys, or other inert conductive substrates that can be loaded with zinc.
Another object of the present invention is a method for preparing the above high concentration solution, specifically as follows:
reacting ZnCl2，ZnBr2Adding deionized water into a container, mixing, and controlling the concentration of zinc ions at 35mol kg-1Hereinafter, solutions of two solutes of zinc chloride and zinc bromide were obtained. Wherein, in the mixing process, the mixture can be properly heated (40-100 ℃ and 2-24 hours) and stirred to promote the dissolution.
Reacting ZnCl2，ZnBr2And deionized water into a container, mixing and adding anhydrous Zn (OAc)2And after being uniformly stirred, the mixture is heated for more than 2 hours at the temperature of 100-120 ℃ to obtain three solute solutions of zinc chloride, zinc bromide and zinc acetate. Wherein, in ZnCl2，ZnBr2The mixture of (2) can be heated (40-100 ℃ C., 2-24 hours) and stirred to promote dissolution. Experiments prove that the concentration of zinc ions in the three-system solution is 50mol kg-1The concentration of acetic acid high ion is 10mol kg-1Hereinafter, the electrolyte can be used as a liquid electrolyte while maintaining a liquid phase state. Thus, by Zn (OAc)2The zinc ion concentration of the zinc ion is 35 to 50mol kg-1The solution of (1).
The invention has the beneficial effects that: the hybrid solute system has the property that any single component does not have, and the solubility of the hybrid solute system in water is far higher than that of single zinc chloride, zinc bromide or zinc acetate. Bis consisting of zinc bromide and zinc chlorideThe high concentration of the component solution is derived from the effect of 'multi-salt co-dissolution', i.e. the high-concentration salt solution acts as a new solvent to dissolve another unhydrated salt and form a new 'dissolved salt mixture'. The formation of ultra-concentrated zinc chloride-zinc bromide-zinc acetate-water "copolymers" is based on another mechanism: when a large amount of electrolyte salt dissolved in water at a high temperature is cooled to room temperature, the electrolyte salt cannot continue to grow by aggregation due to the "end capping" of acetate ions, and further, inorganic oligomers with a large molecular weight stably exist in the electrolyte solution rather than being precipitated as grains. The latter mechanism of formation is distinct from known "salt in water" and "water in salt" electrolytes, and its discovery breaks the electrolyte concentration limit achievable by conventional dissolution routes and can be considered a "third class aqueous electrolyte". The various super-concentrated electrolytes not only effectively inhibit the electrolysis of water, but also reduce the oxidation potential of bromide ions, further promote the intercalation of bromine in the anode material, realize the first-order intercalation of bromine in the anode material, and greatly improve the specific discharge capacity (about 638mAh g) of the anode-1) And coulombic efficiency. Due to the extremely high ion concentration in the electrolyte, the assembled double-ion battery has high specific energy density, simple preparation and low cost, and has important application prospect in the large-scale fixed grid-level electrochemical energy storage market.
In the present invention, unless otherwise specified, the concentration is expressed by solute-solvent ratio, and is 60 to 100mol kg-1The amount of solute dissolved in water is 60-100 mol per kilogram.
Drawings
FIG. 1 is a mass spectrum of the salt-water "copolymer" of example 1, from which it can be seen that there are a number of molecular ion peaks in solution with relative molecular masses greater than any component in the system, indicating the presence of oligomers in the salt-water "copolymer".
Fig. 2 is a photograph of the salt-water "copolymer" electrolyte of example 1 and its precursors, as seen from the figure, of a mixture of salts formed from a molar ratio of 33.75: 11.25: 1, zinc chloride, zinc bromide and zinc acetate in a specific stoichiometric ratio with a small amount of water can form a colorless transparent salt-water "copolymer" stable at room temperature after heating.
FIG. 3 is a constant current charge and discharge diagram of the battery of example 1, which is shown at 1A g-1The specific charge-discharge capacity under the current density is more than 650mAh g-1And the coulombic efficiency is more than 95 percent.
FIG. 4 is a battery cycle chart of example 1, which is seen at 1A g-1The capacity retention rate after 200 cycles under the current density of (1) is more than 98%.
Fig. 5 is a photograph of the electrolyte and its precursor of example 2, and it can be seen that the ratio of the molar ratio of 28: 14: 1, zinc chloride, zinc bromide and zinc acetate in a specific stoichiometric ratio with a small amount of water can form a colorless transparent salt-water "copolymer" stable at room temperature after heating.
Fig. 6 is a photograph of the aqueous eutectic salt electrolyte and its precursor of example 3, which is seen from the graph of the molar ratio of 3: 1, the zinc chloride and the zinc bromide are mixed with a small amount of water according to a specific stoichiometric ratio and heated to form colorless transparent water-phase eutectic salt which is stable at room temperature.
Fig. 7 is a photograph of the salt-water "copolymer" electrolyte of example 4 and its precursors, as seen from the figure, of a mixture of salts formed from a mixture of salts formed in a molar ratio of 22.5: 22.5: 1, zinc chloride, zinc bromide and zinc acetate in a specific stoichiometric ratio with a small amount of water can form a colorless transparent salt-water "copolymer" stable at room temperature after heating.
FIG. 8 is the electrochemical in-situ Raman spectrum of the macroscopic anode material-graphene film anode in the salt-water copolymer of example 1, from which it can be seen that the G peak position of graphene in the charging process is 1579cm-1It becomes 1625cm-1Represents the formation of an I-stage Br intercalated graphite compound; the G peak is changed back to 1579cm during the discharging process-1The charging and discharging process is proved to be completely reversible.
Fig. 9 is an electrochemical in situ XRD spectrum of the macroscopic cathode material-graphene film cathode in salt-water "copolymer" of example 1, from which it can be seen that the (002) plane peak position of graphene changes from the original 26.5 ° to 25.3 ° during charging, representing the formation of I-stage Br intercalated graphite compound; the temperature is changed back to 26.3 degrees in the discharging process, and the charging and discharging process is proved to be completely reversible.
Detailed Description
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are all within the scope of the present invention.
Example 1:
(1) adding 0.3375mol of zinc chloride and 0.1125mol of zinc bromide into 10g of deionized water in sequence, and then heating for 2h at the temperature of 60 ℃ to obtain the zinc chloride-zinc complex2、ZnBr2And water. Adding 0.01mol zinc acetate, heating in a 120 ℃ oven for 2h, and naturally cooling to obtain the total concentration of 46mol kg-1The zinc chloride-zinc bromide-zinc acetate-water copolymer solution of (1), wherein the molar ratio of bromide ions to chloride ions is 1:3, as shown in figure 2.
(2) And (3) sequentially overlapping the zinc cathode, the glass fiber diaphragm soaked with the electrolyte in the step (1) and the graphene film anode into a battery mould for pressurization and heat sealing.
The cell obtained by the above procedure is at 1A g-1The specific discharge capacity of the alloy is 607.5mAh g-1(see fig. 3, calculated based on the positive electrode active material), and has excellent cycle stability with a capacity retention rate of more than 98% after 200 charge-discharge cycles (see fig. 4).
In-situ Raman and X-ray diffraction patterns of the graphene film anode in the charging and discharging processes of the battery are respectively shown in figures 8 and 9, and it can be seen that the G peak position of graphene in the charging process is 1579cm-1It becomes 1625cm-1Represents the formation of an I-stage Br intercalated graphite compound; the G peak is changed back to 1579cm during the discharging process-1The charging and discharging process is proved to be completely reversible. According to an electrochemical in-situ XRD spectrogram, the (002) plane peak position of the graphene is changed from the original 26.5 degrees to 25.3 degrees in the charging process, which represents the formation of an I-stage Br intercalation graphite compound; the temperature is changed back to 26.3 degrees in the discharging process, and the charging and discharging process is proved to be completely reversible.
According to the nernst equation:
E＝Eo-RT/zF·ln(α[R]/α[O])
the redox potential of the anion is:
Eanion＝Eo-RT/zF·ln(c[anion]/γ[anion])
the improvement of the total ion concentration in the electrolyte reduces the oxidation potential of bromide ions, improves the reduction potential of zinc ions, further avoids the occurrence of the side reaction of oxygen evolution and hydrogen evolution of water molecules, is favorable for inhibiting the shuttle effect of halogen, and promotes the intercalation of the halogen in a macroscopic anode material.
The combination of electrochemical in-situ Raman and X-ray diffraction technologies (figures 8-9) proves that the bromine realizes I-stage intercalation in the graphite anode in the charging process, so that the battery anode is endowed with high specific capacity.
Example 2:
(1) adding 0.28mol of zinc chloride and 0.14mol of zinc bromide into 10g of deionized water in sequence, and then heating for 24 hours at 40 ℃ to obtain the zinc bromide zinc complex2、ZnBr2And water. Adding 0.01mol zinc acetate, heating in an oven at 100 deg.C for 10h, and naturally cooling to obtain total concentration of 43mol kg-1The zinc chloride-zinc bromide-zinc acetate-water copolymer solution of (1) is shown in figure 5, wherein the molar ratio of bromide ions to chloride ions is 1: 2.
(2) And (3) sequentially overlapping the graphene fiber non-woven fabric negative electrode substrate, the glass fiber diaphragm soaked with the electrolyte in the step (1) and the expanded graphite positive electrode into a battery mould for pressurization and heat sealing.
The cell obtained by the above procedure is at 1A g-1Has a specific discharge capacity of 632mAh g at the current density of (2)-1(calculated based on the positive electrode active material), and has better cycle stability, and the capacity retention rate is more than 90 percent after 200 charge-discharge cycles.
In-situ Raman test and XRD test are carried out on the expanded graphite anode in the charging and discharging processes of the battery, and analysis is carried out according to the example 1, which proves that the bromine at the concentration also realizes I-stage intercalation in the expanded graphite anode, thereby endowing the battery anode with high specific capacity.
Example 3:
(1) adding 0.245mol of zinc chloride and 0.245mol of zinc bromide into 10g of deionized water in sequence, and then heating for 2h at 100 ℃ to obtain the zinc bromide zinc complex2、ZnBr2And water. Adding 0.05mol of zinc acetate, continuously heating in a 120 ℃ oven for 72h, and naturally cooling to obtain 50mol kg of total concentration-1The zinc chloride-zinc bromide-zinc acetate-water copolymer solution of (1) is shown in figure 6, wherein the molar ratio of bromide ions to chloride ions is 1: 1.
(2) And (3) sequentially overlapping the carbon cloth negative electrode substrate, the glass fiber diaphragm soaked with the electrolyte in the step (1) and the middle-phase microsphere graphite positive electrode into a battery mould for pressurization and heat sealing.
The cell obtained by the above procedure is at 1A g-1Has a specific discharge capacity of 637mAh g at the current density of (1)-1(calculated based on the positive electrode active material), and has better cycle stability, and the capacity retention rate is more than 85 percent after 200 charge-discharge cycles.
In-situ Raman test and XRD test are carried out on the middle-phase microsphere graphite anode in the charging and discharging processes of the battery, and analysis is carried out according to the example 1, which proves that the bromine at the concentration also realizes I-stage intercalation in the middle-phase microsphere graphite anode, so that the battery anode is endowed with high specific capacity.
Example 4:
(1) sequentially adding 0.2625mol of zinc chloride and 0.0875mol of zinc bromide into 10g of deionized water, heating for 2h at 60 ℃, and naturally cooling to obtain the total concentration of 35mol kg-1The zinc chloride-zinc bromide aqueous eutectic salt solution of (1) wherein the molar ratio of bromide ions to chloride ions is 1:3, see fig. 7.
(2) And (3) sequentially overlapping the zinc cathode, the glass fiber diaphragm soaked with the electrolyte in the step (1) and the artificial graphite anode into a battery mould for pressurization and heat sealing.
The cell obtained by the above procedure is at 1A g-1The specific discharge capacity of the alloy is 382mAh g-1(calculated based on the positive electrode active material) and has good cycle stability after 200 charge-discharge cyclesThe capacity retention rate is more than 80%.
Example 5:
(1) adding 0.225mol of zinc chloride and 0.075mol of zinc bromide into 10g of deionized water, and heating at 60 ℃ for 2h to obtain a total concentration of 30mol kg-1The zinc chloride-zinc bromide aqueous phase co-dissolved salt solution of (1), wherein the molar ratio of bromide ions to chloride ions is 1: 3.
(2) And (3) sequentially overlapping the zinc cathode, the glass fiber diaphragm soaked with the electrolyte in the step (1) and the asphalt-based graphite anode into a battery mould for pressurization and heat sealing.
The cell obtained by the above procedure is at 1A g-1The specific discharge capacity of the alloy is about 350mAh g under the current density of (1)-1(calculated based on the positive electrode active material), the capacity retention rate after 200 charge-discharge cycles is more than 70%.
Claims (9)
1. A high-concentration solution is characterized in that the solution is an aqueous solution, and at least zinc ions, bromide ions and chloride ions are contained in the solution, wherein the concentration of the zinc ions is 30mol kg-1Above, concentration refers to the amount of solute species dissolved per kilogram of water; also comprises acetate ions, and the concentration of zinc ions is 50mol kg-1The concentration of acetate ions is 10mol kg-1The following.
2. The solution of claim 1, wherein the concentration of bromide ions is in the range of 15 to 90mol kg-1The concentration range of the chloride ions is 15-90 mol kg-1。
3. The solution of claim 1, wherein the ratio of bromide ion to chloride ion concentration is 1: 3.
4. the solution of claim 1, wherein the ratio of bromide ion to chloride ion concentration is 1: 3.
5. use of a solution according to any one of claims 1 to 4 as a battery electrolyte.
6. Use according to claim 5, characterised in that the concentration of zinc ions in the electrolyte is 46mol kg-1The concentration ratio of bromide ions, chloride ions and acetate is 11.25: 33.75: 1.
7. a method for preparing a solution according to claim 1, characterized in that it comprises at least: reacting ZnCl2，ZnBr2And deionized water into the vessel, mixing, adding anhydrous Zn (OAc)2And after being uniformly stirred, the mixture is heated for more than 2 hours at the temperature of 100-120 ℃.
8. The method according to claim 7, wherein the concentration of the bromide ion is in the range of 15 to 90mol kg-1The concentration range of the chloride ions is 15-90 mol kg-1The concentration of zinc ions is 50mol kg-1The concentration of acetate ions is 10mol kg-1The following.
9. The method according to claim 7, wherein the concentration ratio of bromide ions to chloride ions is 1: 3.
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