CN117832660A - Surfactant-free microemulsion electrolyte and battery using same - Google Patents
Surfactant-free microemulsion electrolyte and battery using same Download PDFInfo
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- CN117832660A CN117832660A CN202410207471.3A CN202410207471A CN117832660A CN 117832660 A CN117832660 A CN 117832660A CN 202410207471 A CN202410207471 A CN 202410207471A CN 117832660 A CN117832660 A CN 117832660A
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- free microemulsion
- zinc
- amphiphilic
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 97
- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 71
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 235000020075 ouzo Nutrition 0.000 claims abstract description 6
- 230000006698 induction Effects 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FZQFNTYKHHDUFT-UHFFFAOYSA-N nitric acid;propan-1-amine Chemical compound CCCN.O[N+]([O-])=O FZQFNTYKHHDUFT-UHFFFAOYSA-N 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 210000004027 cell Anatomy 0.000 description 20
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 230000008021 deposition Effects 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a surfactant-free microemulsion electrolyte and a battery using the same, wherein the surfactant-free microemulsion electrolyte comprises an amphiphilic substance, a hydrophobic solvent and water; the amphiphilic substance is one or more of amphiphilic salt, amphiphilic organic solvent and amphiphilic ionic liquid; the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.1-20 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 1-99%; under the induction of the ouzo effect, the amphiphilic substance enables the hydrophobic solvent which is not mutually soluble to be mutually soluble with water to form surfactant-free microemulsion electrolyte, and forms a Mobius-type characteristic solvated cluster in the surfactant-free microemulsion electrolyte; the characteristic solvated clusters are water-in-oil type; can inhibit the activity of free water and solvated water, can solve the occurrence of side reaction, and remarkably improves the performance of the zinc ion secondary battery.
Description
Technical Field
The invention belongs to the technical field of zinc ion secondary batteries, and particularly relates to surfactant-free microemulsion electrolyte and a battery using the same.
Background
In recent years, the need for efficient and environmentally friendly energy storage systems has driven the rapid development of rechargeable batteries. Among the various battery technologies, zinc ion batteries are considered as a promising alternative for post-lithium era grid scale energy storage applications due to their high energy density, low cost and abundant zinc resources. However, practical application of aqueous zinc ion batteries presents challenges, particularly the problem of poor anode and cathode reversibility, which require extensive research and development. In addition, the main reason for the poor reversibility of aqueous zinc ion batteries is that H in the electrolyte 2 Reactivity of O and H 2 O-dominated solvated structure. Although water is a cost-effective, high-reserves solvent, it also presents a number of challenges. During the charge and discharge of the battery, H 2 O readily undergoes hydrogen evolution reactions at the zinc surface, leading to interface corrosion, by-product formation and dendrite growth. In addition, H 2 The relatively high melting point and low boiling point of O makes aqueous zinc ion batteries challenging to operate at low temperature conditions. Researchers have proposed targeted solutions, such as by designing protective layers, regulating zinc ion deposition, current collector modification, separator design, negative electrode alloying, optimizing electrolytes, etc. The electrochemical performance of the aqueous zinc ion battery is greatly improved, but a plurality of technical problems are still unsolved. Adverse side reactions with electrolyte still occur after the battery is assembled and during transportation and storage before use, which seriously affects the practical application of zinc ion batteries. To overcome these limitations and release the full potential of zinc ion batteries, electrolyte optimization and design is an effective approach. Development of an electrolyte having high stability by designing an electrolyte system to effectively suppress H 2 O-related side reactions can realize zinc ion batteries with long service lives.
Disclosure of Invention
In order to solve the problems, the invention provides the surfactant-free microemulsion electrolyte and the battery using the same, wherein the surfactant-free microemulsion electrolyte can inhibit the activities of free water and solvated water, can solve the occurrence of side reactions, remarkably improves the performance of a zinc ion secondary battery, prolongs the service life of the battery, and has good application prospect.
The invention adopts the following technical scheme:
a surfactant-free microemulsion electrolyte comprising an amphiphilic substance, a hydrophobic solvent, and water; the amphiphilic substance is one or more of amphiphilic salt, amphiphilic organic solvent and amphiphilic ionic liquid; the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.1-20 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 1-99%; under the induction of the ouzo effect, the amphiphilic substance enables the hydrophobic solvent which is not mutually soluble to be mutually soluble with water to form surfactant-free microemulsion electrolyte, and forms a Mobius-type characteristic solvated cluster in the surfactant-free microemulsion electrolyte; the characteristic solvated clusters are water-in-oil.
Preferably, the amphiphilic salt is one or more of zinc trifluoromethane sulfonate, zinc bis (trifluoromethylsulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, sodium bis (trifluoromethylsulfonyl) imide, and potassium bis (trifluoromethylsulfonyl) imide; the amphiphilic organic solvent is one or more of tetrahydrofurfuryl alcohol, propanol and ethanol; the amphiphilic ionic liquid is proton ionic liquid propylamine nitrate.
Preferably, the hydrophobic solvent is one or more of a hydrophobic organic solvent and a hydrophobic ionic liquid.
Preferably, the hydrophobic organic solvent is one or more of hydrophobic cyclopentyl methyl ether, methyl ethyl carbonate, diethyl adipate, benzyl alcohol, butyl acetate or diethyl carbonate; the hydrophobic ionic liquid is 1-butyl-3-methylimidazole hexafluorophosphate.
Preferably, the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.3-3 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 30-80%.
A zinc ion secondary battery includes a surfactant-free microemulsion electrolyte, a positive electrode, a negative electrode, and a separator.
Preferably, the positive electrode is NVO; the negative electrode is a zinc sheet; the diaphragm is a glass fiber diaphragm.
Preferably, the positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7-8:1-2:1.
Preferably, the positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7.5:1.5:1.
Preferably, in the positive electrode, the preparation method of the active material NVO comprises the following steps:
dissolving sodium chloride in water to prepare 50-200ml of 1-3mol/L sodium chloride aqueous solution;
adding 1-4g of vanadium pentoxide powder, magnetically stirring at 300-800rpm for 50-100 hours, centrifuging the obtained orange powder, washing with deionized water and ethanol for 2-5 times, and drying at 80-120deg.C for 10-20 hours to obtain active substance NVO.
After the technical scheme is adopted, compared with the background technology, the invention has the following advantages:
1. after amphiphilic substances are added, the hydrophobic solvent which is originally insoluble and water can be mutually dissolved under the induction of the ouzo effect to form surfactant-free microemulsion electrolyte, and the surfactant-free microemulsion electrolyte forms Mobius characteristic solvation clusters, so that the water-in-oil characteristic solvation clusters can well limit water activity, effectively inhibit side reactions, destroy the original water molecule network and the like, and finally the performance and the cycle life of the zinc ion secondary battery are greatly improved.
2. Compared with the water-based electrolyte, the surfactant-free microemulsion-type electrolyte provided by the invention can form an effective interface layer, the kinetics process is regulated and controlled to guide zinc ions to be uniformly deposited, the low-temperature performance of the battery is improved, the performance of the zinc ion secondary battery is improved, and the service life of the battery is prolonged.
Drawings
FIG. 1 is a Raman spectrum diagram of a surfactant-free microemulsion electrolyte of a zinc ion secondary battery prepared in example 1;
FIG. 2 is a graph showing that the zinc-zinc symmetric cell using the surfactant-free microemulsion electrolyte and the aqueous electrolyte of the zinc ion secondary battery of example 2 was at 1mA/cm 2 Cycling performance plot at constant current;
FIG. 3 is a graph showing that the zinc-zinc symmetric cell using the surfactant-free microemulsion electrolyte and the aqueous electrolyte of the zinc ion secondary battery of example 2 was at 5mA/cm 2 Cycling performance plot at constant current;
FIG. 4 is a graph showing the cycling performance of a positive electrode (NVO) -zinc full cell at a current density of 5A/g using a surfactant-free microemulsion electrolyte and an aqueous electrolyte for a zinc ion secondary battery of example 2;
FIG. 5 is a graph of the cycling performance of a positive electrode (NVO) -zinc full cell using a surfactant-free microemulsion electrolyte for a zinc ion secondary battery of example 2 at a temperature of-30 ℃ and a current density of 5A/g;
FIG. 6 shows a zinc-copper half cell at 1mA/cm using a surfactant-free microemulsion electrolyte and an aqueous electrolyte for a zinc ion secondary battery in example 2 2 Cycling performance plot at current;
FIG. 7 is a graph showing that the zinc-zinc symmetric cell using the surfactant-free microemulsion electrolyte and the aqueous electrolyte of the zinc ion secondary battery of example 2 was at 1mA/cm 2 XRD test pattern of zinc surface after 50 cycles of constant current;
FIG. 8 shows a zinc-zinc symmetric cell at 1mA/cm using a surfactant-free microemulsion electrolyte and an aqueous electrolyte of a zinc ion secondary battery in example 2 2 SEM test pattern of zinc surface after 50 cycles of constant current.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1 to 8, a surfactant-free microemulsion electrolyte includes an amphiphilic substance, a hydrophobic solvent, and water; the amphiphilic substance is one or more of amphiphilic salt, amphiphilic organic solvent and amphiphilic ionic liquid; the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.1-20 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 1-99%; under the induction of the ouzo effect, the amphiphilic substance enables the hydrophobic solvent which is not mutually soluble to be mutually soluble with water to form surfactant-free microemulsion electrolyte, and forms a Mobius-type characteristic solvated cluster in the surfactant-free microemulsion electrolyte; the characteristic solvated clusters are water-in-oil.
The amphiphilic salt is one or more of zinc trifluoromethane sulfonate, zinc bis (trifluoromethylsulfonyl) imide, lithium bistrifluoromethane sulfonyl imide, sodium bistrifluoromethane sulfonyl imide and potassium bistrifluoromethane sulfonyl imide; the amphiphilic organic solvent is one or more of tetrahydrofurfuryl alcohol, propanol and ethanol; the amphiphilic ionic liquid is proton ionic liquid propylamine nitrate.
The hydrophobic solvent is one or more of a hydrophobic organic solvent and a hydrophobic ionic liquid.
The hydrophobic organic solvent is hydrophobic cyclopentyl methyl ether; the hydrophobic ionic liquid is 1-butyl-3-methylimidazole hexafluorophosphate.
The concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.3-3 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 30-80%.
A zinc ion secondary battery includes a surfactant-free microemulsion electrolyte, a positive electrode, a negative electrode, and a separator.
The positive electrode is NVO; the negative electrode is a zinc sheet; the diaphragm is a glass fiber diaphragm.
The positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7-8:1-2:1.
The positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7.5:1.5:1.
In the positive electrode, the preparation method of the active material NVO comprises the following steps:
dissolving sodium chloride in water to prepare 50-200ml of 1-3mol/L sodium chloride aqueous solution;
adding 1-4g of vanadium pentoxide powder, magnetically stirring at 300-800rpm for 50-100 hours, centrifuging the obtained orange powder, washing with deionized water and ethanol for 2-5 times, and drying at 80-120deg.C for 10-20 hours to obtain active substance NVO.
Example 1
A surfactant-free microemulsion electrolyte with concentration of 1mol/L and a full battery thereof are prepared by taking cyclopentyl methyl ether and water as solvents and zinc trifluoromethane sulfonate as a solute:
(1) Preparation of electrolyte: in this example 1, the preparation process utilizing the ouzou effect gradually changed the liquid from single phase to multi-phase as the water ratio increased. This example 1 uses the ouzo effect to produce a volume ratio of 3:1 mixing cyclopentyl methyl ether (CPME) with water to obtain electrolyte solvent, adding a certain amount of zinc trifluoromethane sulfonate (Zn (CF) 3 SO 3 ) 2 ) The surfactant-free microemulsion electrolyte of the zinc ion secondary battery with the water-in-oil solvation structure and the concentration of 1mol/L is prepared.
(2) Preparation of positive electrode active material NVO: sodium vanadate (NVO) was synthesized by mixing 3 g of V 2 O 5 The powder was added to 100mL of a 2mol/L sodium chloride solution and magnetically stirred at 400rpm for 72 hours to obtain an orange powder which was washed 3 times with deionized water and ethanol and dried at 80℃for 12 hours to obtain active material NVO.
Pretreatment of current collector: the NVO positive electrode adopts stainless steel foil as a current collector, a stainless steel foil with the width of 10cm is cut from a stainless steel foil roll, the surface and the edge of the stainless steel foil are flattened by using an electric pair roller press, and the stainless steel foil is cleaned for 3 minutes by using alcohol under the power of 40Hz in an ultrasonic manner for 3 times.
And (3) preparation of a binder: PVDF is used as a binder for the NVO positive electrode according to the following formula 1:25, accurately weighing a certain amount of N-methyl pyrrolidone (NMP) and PVDF in a container, and placing the mixture on a magnetic stirrer for stirring and mixing uniformly.
NVO positive electrode according to 7:2:1, accurately weighing a certain amount of active substances NVO, conductive carbon black and polyvinylidene fluoride, sealing the active substances NVO, conductive carbon black and polyvinylidene fluoride in a small beaker by using a sealing film, adding N-methyl pyrrolidone (NMP) until the slurry can be stirred normally, and placing the prepared slurry on a magnetic stirrer to stir for at least 6 hours to obtain the uniformly mixed positive electrode slurry. The slurry was then smeared onto a pretreated stainless steel foil and scraped flat at a constant speed using a 150 μm gap four-sided doctor blade. And (3) placing the stainless steel foil with the slurry in a vacuum oven at 80 ℃ for drying for at least 10 hours, taking out after the stainless steel foil is completely cooled to room temperature, cutting out the pole piece by using a battery pole piece slicer according to the diameter of 12mm, and placing the pole piece in a sealing bag in a dryer for standby.
(3) The preparation process of the negative electrode plate comprises the following steps: after cutting the purchased commercially pure zinc sheet into square pieces of 10cm, the square pieces were fed into an electric pair roller press to flatten the surface and edges of the zinc sheet to a service thickness of 80 μm. Placing into an ultrasonic cleaner, respectively adding acetone, ethanol and deionized water under 40Hz power, ultrasonically cleaning, and drying the cleaned zinc sheet in a vacuum drying oven at 60deg.C for 3 hr. And taking out the cooled zinc sheet, cutting the zinc sheet into pieces, wherein the cutting diameter of the zinc sheet which is directly used is 12mm, and obtaining the usable negative electrode sheet.
(4) The button cell assembling process comprises the following steps: the coin cell assembly process (all operations performed in an air atmosphere) is as follows: (1) The zinc-zinc symmetrical battery is characterized in that a zinc sheet, a glass fiber diaphragm, a zinc sheet and a stainless Steel Sheet (SS) are sequentially placed in a CR2032 negative electrode battery shell, then an elastic sheet is placed, a CR2032 positive electrode battery shell is covered, and the battery is placed in a button battery packaging machine for sealing. (2) The zinc-zinc symmetrical battery comprises a zinc sheet, a glass fiber diaphragm, a copper sheet and a stainless Steel Sheet (SS) which are sequentially arranged in a CR2032 cathode battery shellAnd placing the elastic sheet, covering the CR2032 positive electrode battery shell, and placing the shell into a button battery packaging machine for sealing. (3) positive electrode (NVO) -zinc cell: sequentially placing a zinc sheet, a glass fiber diaphragm, a positive plate and a stainless Steel Sheet (SS) in a CR2032 negative electrode battery shell, then placing an elastic sheet, covering the CR2032 positive electrode battery shell, and placing the CR2032 positive electrode battery shell in a button battery packaging machine for sealing. When sealing, the packaging pressure of the button cell packaging machine needs to be more than 50kg/cm 3 The duration is longer than 1s, wherein when the positive electrode (NVO) -zinc battery is packaged, the packing paper is needed to be arranged above the battery, so that a loop is prevented from being formed outside the battery during packaging, the battery just packaged cannot be used immediately, and the battery is required to be kept stand for more than 2 hours to enable the electrode/electrolyte interface to be fully contacted and then can be tested.
Example 2
Test of electrochemical properties of electrolytes and batteries:
the raman spectrum of the surfactant-free microemulsion electrolyte of the zinc ion secondary battery of example 1 was tested, and the obtained raman spectrum is shown in fig. 1. From the characteristic peaks of water in fig. 1, it can be seen that the activity of water in the electrolyte is greatly suppressed, and various interactions in the electrolyte can be well analyzed against the displacement of other characteristic functional groups.
And (3) carrying out constant current circulation charge and discharge on a zinc-zinc symmetrical battery containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery at a current of 1 milliamp per square centimeter and a large current of 5 milliamps per square centimeter, and observing polarization and stability information. As shown in fig. 2 and 3, the battery using the surfactant-free microemulsion electrolyte can regulate and control the dynamic process to guide the uniform deposition of zinc ions, and remarkably inhibit related side reactions by inhibiting the activities of solvated water and free water, so that the cycle life of the battery is greatly prolonged. Meanwhile, batteries using aqueous electrolytes have failed in a short period of time due to water-related side reactions and zinc dendrites.
The cycling performance of a positive electrode NVO-zinc full cell containing a surfactant-free microemulsion electrolyte of a zinc ion secondary battery at a constant current of 5A/g is shown in FIG. 4. It can be seen from fig. 4 that the full cell containing the surfactant-free microemulsion electrolyte for zinc ion secondary battery still has extremely high capacity after 4000 cycles, and the curve and flatness thereof show little attenuation, indicating extremely high capacity retention. The capacity of the positive electrode NVO-zinc full cell using the aqueous electrolyte is already close to 0 after 1000 circles.
The positive electrode NVO-zinc full cell containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery is tested at the temperature of minus 30 ℃, the cycle curve of the positive electrode NVO-zinc full cell containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery is shown in figure 5, and as can be seen from figure 5, the positive electrode NVO-zinc full cell containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery can still keep stable circulation and higher capacity in the low-temperature environment of minus 30 ℃.
The zinc-copper half cell containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery is charged and discharged in a constant current circulation mode with a current of 1 milliamp per square centimeter, and the stability and reversibility of the zinc deposition and stripping process are observed. As a result, as shown in fig. 6, the zinc-copper half cell using the surfactant-free microemulsion electrolyte always maintains stable and high coulombic efficiency for 1900 cycles, indicating that the highly reversible and stable zinc deposition and stripping process, whereas the zinc-copper half cell using the aqueous electrolyte is not stable and is relatively chaotic, indicating that the very unstable zinc deposition and stripping process occurs.
And (3) charging and discharging a zinc-zinc symmetrical battery containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery for 50 circles at a constant current of 1 milliamp per square centimeter, removing the battery and taking off a pole piece for XRD test, and observing the condition of surface byproducts. As shown in fig. 7, the electrode sheet of the zinc-zinc battery after the circulation using the surfactant-free microemulsion electrolyte showed no by-product formation, while the zinc negative electrode surface using the aqueous electrolyte showed significant basic by-product formation, indicating that the surfactant-free microemulsion electrolyte can significantly inhibit the water decomposition of the negative electrode surface to inhibit the formation of surface by-products.
And (3) carrying out SEM test on a zinc-zinc symmetrical battery containing the surfactant-free microemulsion electrolyte of the zinc ion secondary battery by removing a battery-removed pole piece after the battery is circularly charged and discharged for 50 circles at a constant current of 1 milliamp per square centimeter, and observing dendrite and zinc ion deposition morphology. As shown in fig. 8, the electrode plate deposition morphology after the circulation of the zinc-zinc battery using the surfactant-free microemulsion electrolyte is flat and compact and dendrite formation is not seen, while the zinc negative electrode surface using the aqueous electrolyte has obvious holes and dendrites due to uneven deposition of zinc ions. The surfactant-free microemulsion electrolyte can regulate and control the dynamic process to guide the uniform deposition of zinc ions.
As shown in Table 1, the versatility of the present invention is further illustrated by testing several hydrophobic organic solvents. The hydrophobic methyl ethyl carbonate, diethyl adipate, benzyl alcohol, butyl acetate and diethyl carbonate can be used for preparing the surfactant-free microemulsion electrolyte with water and zinc trifluoromethane sulfonate.
TABLE 1 test results of several other hydrophobic organic solvents
| Hydrophobic organic solvent species | Whether or not a surfactant-free microemulsion-type electrolyte can be prepared |
| Methyl ethyl carbonate | √ |
| Adipic acid diethyl ester | √ |
| Benzyl alcohol | √ |
| Butyl acetate | √ |
| Diethyl carbonate | √ |
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A surfactant-free microemulsion electrolyte is characterized in that: the surfactant-free microemulsion electrolyte comprises an amphiphilic substance, a hydrophobic solvent and water; the amphiphilic substance is one or more of amphiphilic salt, amphiphilic organic solvent and amphiphilic ionic liquid; the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.1-20 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 1-99%; under the induction of the ouzo effect, the amphiphilic substance enables the hydrophobic solvent which is not mutually soluble to be mutually soluble with water to form surfactant-free microemulsion electrolyte, and forms a Mobius-type characteristic solvated cluster in the surfactant-free microemulsion electrolyte; the characteristic solvated clusters are water-in-oil.
2. A surfactant-free microemulsion electrolyte as defined in claim 1, wherein: the amphiphilic salt is one or more of zinc trifluoromethane sulfonate, zinc bis (trifluoromethylsulfonyl) imide, lithium bistrifluoromethane sulfonyl imide, sodium bistrifluoromethane sulfonyl imide and potassium bistrifluoromethane sulfonyl imide; the amphiphilic organic solvent is one or more of tetrahydrofurfuryl alcohol, propanol and ethanol; the amphiphilic ionic liquid is proton ionic liquid propylamine nitrate.
3. A surfactant-free microemulsion electrolyte as defined in claim 1, wherein: the hydrophobic solvent is one or more of a hydrophobic organic solvent and a hydrophobic ionic liquid.
4. A surfactant-free microemulsion electrolyte according to claim 3, wherein: the hydrophobic organic solvent is one or more of hydrophobic cyclopentyl methyl ether, methyl ethyl carbonate, diethyl adipate, benzyl alcohol, butyl acetate or diethyl carbonate; the hydrophobic ionic liquid is 1-butyl-3-methylimidazole hexafluorophosphate.
5. A surfactant-free microemulsion electrolyte as defined in claim 1, wherein: the concentration of the amphiphilic substance in the surfactant-free microemulsion electrolyte is 0.3-3 mol/L; the volume fraction of the hydrophobic solvent in the surfactant-free microemulsion electrolyte is 30-80%.
6. A zinc ion secondary battery characterized in that: the zinc ion secondary battery comprises surfactant-free microemulsion electrolyte, a positive electrode, a negative electrode and a diaphragm; wherein the surfactant-free microemulsion electrolyte is the surfactant-free microemulsion electrolyte of any one of claims 1-5.
7. The zinc ion secondary battery according to claim 6, wherein: the positive electrode is NVO; the negative electrode is a zinc sheet; the diaphragm is a glass fiber diaphragm.
8. The zinc ion secondary battery according to claim 7, wherein: the positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7-8:1-2:1.
9. The zinc ion secondary battery according to claim 8, wherein: the positive electrode comprises active material NVO, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7.5:1.5:1.
10. The zinc-ion secondary battery according to claim 9, wherein in the positive electrode, the method for producing active material NVO comprises the steps of:
dissolving sodium chloride in water to prepare 50-200ml of 1-3mol/L sodium chloride aqueous solution;
adding 1-4g of vanadium pentoxide powder, magnetically stirring at 300-800rpm for 50-100 hours, centrifuging the obtained orange powder, washing with deionized water and ethanol for 2-5 times, and drying at 80-120deg.C for 10-20 hours to obtain active substance NVO.
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