CN117832652A - Additive for aqueous zinc ion battery electrolyte, electrolyte and aqueous zinc ion battery - Google Patents
Additive for aqueous zinc ion battery electrolyte, electrolyte and aqueous zinc ion battery Download PDFInfo
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- CN117832652A CN117832652A CN202311793081.0A CN202311793081A CN117832652A CN 117832652 A CN117832652 A CN 117832652A CN 202311793081 A CN202311793081 A CN 202311793081A CN 117832652 A CN117832652 A CN 117832652A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 132
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000654 additive Substances 0.000 title claims abstract description 39
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 98
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- -1 fluoro amino Chemical group 0.000 claims abstract description 18
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical group 0.000 claims abstract description 5
- 150000001413 amino acids Chemical class 0.000 claims abstract description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 33
- 229960001763 zinc sulfate Drugs 0.000 claims description 31
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 31
- VLCYCQAOQCDTCN-UHFFFAOYSA-N eflornithine Chemical compound NCCCC(N)(C(F)F)C(O)=O VLCYCQAOQCDTCN-UHFFFAOYSA-N 0.000 claims description 20
- QFGMPXZFCIHYIR-UHFFFAOYSA-N 2-azaniumyl-3-(3,5-difluorophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC(F)=CC(F)=C1 QFGMPXZFCIHYIR-UHFFFAOYSA-N 0.000 claims description 8
- UYTSRQMXRROFPU-UHFFFAOYSA-N 2-azaniumyl-3-fluoropropanoate Chemical compound FCC(N)C(O)=O UYTSRQMXRROFPU-UHFFFAOYSA-N 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 12
- 238000004090 dissolution Methods 0.000 abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000843 powder Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an additive for an electrolyte of a water-based zinc ion battery, the electrolyte and the water-based zinc ion battery, and belongs to the technical field of water-based zinc ion batteries. The electrolyte additive is water-soluble fluorinated amino acid, and the current density of the water-based zinc ion battery is 5-10 mA cm ‑2 The positive electrode material of the water-based zinc ion battery is a transition metal-based positive electrode material. The fluoro amino acid additive provided by the invention effectively solves the problems of generation of microcracks of positive electrode material particles, dissolution of transition metal ions and corrosion of zinc dendrites and zinc, has the advantages of simple preparation process, high safety, environmental friendliness and the like, and has a wide application prospect in the field of water-based zinc ion batteries.
Description
Technical Field
The invention relates to an additive for an electrolyte of a water-based zinc ion battery, the electrolyte and the water-based zinc ion battery, and belongs to the technical field of water-based zinc ion batteries.
Background
Aqueous Zinc Ion Batteries (AZIBs) are considered as one of the most promising alternatives to lithium ion batteries because of their advantages of high theoretical capacity, abundant resources, low cost, high safety, etc., and have been attracting attention from researchers in recent years.
However, both the positive electrode material and the negative electrode material are important factors limiting the further development of the aqueous zinc ion battery. Wherein, the negative electrode material is mainly due to hydrogen evolution reaction and zinc dendrite formation. The hydrogen evolution reaction consumes electrons for zinc deposition during charging, resulting in a decrease in coulombic efficiency of zinc ion deposition/dissolution. On the other hand, HER can irreversibly consume electrolyte, thereby reducing the service life of the battery, and simultaneously precipitating H along with the decomposition of the electrolyte 2 The battery expands and even explodes with the increasing internal pressure, thereby affecting the safe use of the battery. Furthermore, due to HER reaction accompanying OH - The generation of (2) changes the local pH in the electrolyte, thereby generating Zn 4 SO 4 (OH) 6 ·xH 2 O、Zn(OH) 2 And ZnO and other byproducts. The zinc dendrite mainly affects the performance of the battery in the following two aspects, firstly, in the process of repeatedly charging the battery, the generated zinc dendrite easily drops off from the surface of a zinc cathode to form dead zinc which does not participate in the electrode reaction, thereby affecting the capacity and coulomb efficiency of the battery. On the other hand, the zinc dendrites generated easily pierce the separator, short-circuiting the battery, and causing safety problems. Currently, the current research focus of zinc ion battery cathode materials is manganese-based materials and vanadium-based materials. Due to Zn 2+ Larger ionic radius, zn with charge-discharge cycle 2+ The cathode material is continuously embedded into/separated from the current collector, so that the structural change of the cathode material is easy to cause the cathode material on the surface of the current collector to fall off, and the performance of the battery is influenced. In addition, as the charge-discharge cycle of the battery proceeds, transition metal ions such as Mn, V are eluted from the positive electrode material, resulting in collapse of the positive electrode material structure, thereby affecting the battery performance.
So far, scientific researchers have proposed various strategies for solving the problems encountered in the aqueous zinc ion battery, including material structural design, material surface modification and electrolyte engineering optimization, wherein the electrolyte additive is a modification means hopeful to realize large-scale application due to simple process and low cost. In consideration of the complexity of the problems of the water-based zinc ion battery, development of a multifunctional electrolyte additive and simultaneous realization of suppression of structural collapse of a positive electrode side material, dissolution of transition metal ions, hydrogen evolution reaction of a negative electrode side and zinc dendrite are key to realization of rapid development of the water-based zinc ion battery.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an additive for an aqueous zinc ion battery electrolyte, an electrolyte, and an aqueous zinc ion battery, which can simultaneously inhibit dissolution of a transition metal ion on the positive electrode side, hydrogen evolution reaction on the negative electrode side, and zinc dendrite.
In order to achieve the above object, the technical scheme of the present invention is as follows.
An electrolyte additive for a water-based zinc ion battery, wherein the electrolyte additive is water-soluble fluorinated amino acid, and the current density of the water-based zinc ion battery is 5-10 mA cm -2 The positive electrode material of the water-based zinc ion battery is a transition metal-based positive electrode material.
Preferably, the water-soluble fluoroamino acid is difluoromethylornithine, 3-fluoroalanine or 3, 5-difluorophenylalanine.
An electrolyte for an aqueous zinc ion battery, the electrolyte comprising a soluble zinc salt, H 2 O and additives according to the invention.
Preferably, in the electrolyte, the soluble zinc salt is one or more of zinc sulfate, zinc sulfate hydrate, zinc chloride and its hydrate, zinc trifluoromethane sulfonate and its hydrate. More preferably, the soluble zinc salt is zinc sulfate.
Preferably, the molar concentration of the soluble zinc salt in the electrolyte is 1-3 mol/L. Most preferably 2mol/L.
Preferably, the molar concentration of the additive in the electrolyte is 1-20 mmol/L. More preferably, the molar concentration of the additive is 8-12 mmol/L.
Preferably, the electrolyte further comprises a manganese ion additive. More preferably, the manganese ion additive is one or more of manganese nitrate, manganese sulfate and manganese chloride. Most preferred is manganese sulfate.
Preferably, in the electrolyte, the molar concentration of the manganese ion additive is 0.05-0.5 mol/L. Most preferably 0.1mol/L.
The invention relates to a water-based zinc ion battery, which comprises electrolyte, a transition metal-based positive electrode material, a negative electrode material and a diaphragm.
Preferably, the negative electrode material comprises zinc sheets, zinc foils, zinc powder and foam zinc. Most preferred is a commercial zinc foil having a thickness of 100 nm.
Preferably, the positive electrode material is lithium manganate, manganese dioxide, vanadium pentoxide or sodium vanadate. Most preferred is sodium vanadate.
Preferably, the separator is glass fiber.
Advantageous effects
The invention uses water-soluble fluoro amino acid as the additive of the water-based zinc ion battery, on one hand, zn can be changed 2+ Is solvated in structure, the carboxyl group will partially replace Zn 2+ The water molecules in the solvated shell layer reduce the water molecule content in the zinc complex, thereby inhibiting hydrogen evolution reaction, corrosion passivation and generation of by-product basic zinc sulfate, on the other hand, under high current density, the additive can be adsorbed on the surface of a zinc negative electrode, and a layer of ZnF is generated on the surface of the zinc negative electrode in the circulating process 2 An inorganic layer for reducing the local current density of the surface of the zinc cathode and regulating Zn 2+ Is effective in inhibiting dendrite growth.
The invention uses water-soluble fluoro amino acid as the water-based zinc ion battery additive, and the additive can generate a layer of fluorine-rich CEI film on the surface of the positive electrode material in situ in the battery charging and discharging cycle process, thereby effectively stabilizing the structure of the positive electrode material, inhibiting the structural collapse of the positive electrode material and the dissolution of transition metal ions in the positive electrode material, and further improving the cycle stability of the battery.
Drawings
FIG. 1 is a graph of the contact angle of a 2mol/L zinc sulfate solution of comparative example 1 and a modified electrolyte of example 2 having a concentration of 10mmol/L difluoromethylornithine on a commercial zinc foil substrate.
FIG. 2 shows that the Zn symmetry cells obtained in application example 2 and comparative application example 1 had a current density of 5mAcm -2 The surface capacity is 1mAh cm -2 Cycling performance graph under conditions.
FIG. 3 is a Zn symmetric cell obtained in application example 2 and comparative application example 1, at a current density of 1mA cm -2 The surface capacity is 1mAh cm -2 XPS plot of zinc negative electrode surface after 50 weeks of cycling under conditions.
FIG. 4 is a Zn symmetric cell obtained in application example 2 and comparative application example 1, at a current density of 1mA cm -2 The surface capacity is 1mAh cm -2 SEM images of the zinc negative electrode surface after 50 weeks of cycling under conditions.
Fig. 5 is a graph of the rate performance of Zn NVO full cells obtained in application example 2 and comparative application example 1.
FIG. 6 shows that the Zn NVO full cells obtained in application example 2 and comparative application example 1 were measured at 2Ag -1 Cycling performance plot at current density.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the following examples, which are intended to illustrate the present invention only, and it is apparent that the described examples are intended to be illustrative of only some, but not all, of the present invention. All other embodiments, based on the embodiments herein, which a person of ordinary skill in the art would obtain without undue effort, are within the scope of the present application.
Example 1
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 4.55mg of difluoromethyl ornithine powder, adding into the zinc sulfate solution obtained in the step (1), and stirring at 25deg.C until the powder is completely dissolved to obtain difluoromethyl birdModified electrolyte with 5mmol/L of amino acid concentration, which is marked as ZnSO 4 +5mM DFMO。
Example 2
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) 9.1mg of difluoromethylornithine powder is weighed and added into the zinc sulfate solution obtained in the step (1), and the mixture is fully stirred at 25 ℃ until the mixture is completely dissolved, so as to obtain a modified electrolyte with the concentration of difluoromethylornithine of 10mmol/L, which is marked as ZnSO 4 +10mM DFMO。
Example 3
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 18.2mg of difluoromethylornithine powder, adding into the zinc sulfate solution obtained in the step (1), and stirring at 25 ℃ until the powder is completely dissolved to obtain a modified electrolyte with 20mmol/L difluoromethylornithine concentration, which is named as ZnSO 4 +20mM DFMO。
Example 4
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 2.68mg of 3-fluoroalanine powder, adding into the zinc sulfate solution obtained in the step (1), stirring thoroughly at 25deg.C to obtain a modified electrolyte with 3-fluoroalanine concentration of 5mmol/L, denoted as ZnSO 4 +5mM 3-FDA。
Example 5
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 5.354mg of 3-fluoroalanine powder, adding into the zinc sulfate solution obtained in step (1), stirring at 25deg.C until completely dissolved to obtain a modified electrolyte with 3-fluoroalanine concentration of 10mmol/L, and recording as ZnSO 4 +10mM 3-FDA。
Example 6
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 10.71mg of 3-fluoroalanine powder, adding into the zinc sulfate solution obtained in the step (1), and stirring at 25deg.C until the powder is completely dissolved to obtain a modified electrolyte with 3-fluoroalanine concentration of 20mmol/L, which is denoted as ZnSO 4 +20mM 3-FDA。
Example 7
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 5.03mg of 3, 5-difluorophenylalanine powder, adding the powder into the zinc sulfate solution obtained in the step (1), and fully stirring at 25 ℃ until the powder is completely dissolved to obtain a modified electrolyte with the concentration of 3, 5-difluorophenylalanine of 5mmol/L, which is recorded as ZnSO 4 +5mM 3,5-DDL。
Example 8
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 10.06mg of 3, 5-difluorophenylalanine powder, adding into the zinc sulfate solution obtained in the step (1), fully stirring at 25 ℃ until the powder is completely dissolved to obtain a modified electrolyte with the concentration of 3, 5-difluorophenylalanine of 10mmol/L, and marking the modified electrolyte as ZnSO 4 +10mM 3,5-DDL。
Example 9
A water-based zinc ion battery electrolyte of a fluoro amino acid additive, a preparation method and application thereof, comprising the following steps:
(1) Weigh 2.88g of solid ZnSO 4 ·7H 2 O was added to 3.68ml of deionized water and stirred well until completely dissolved, to give a zinc sulfate solution having a concentration of 2mol/L.
(2) Weighing 20.12mg of 3, 5-difluorophenylalanine powder, adding the powder into the zinc sulfate solution obtained in the step (1), and fully stirring at 25 ℃ until the powder is completely dissolved to obtain a modified electrolyte with the concentration of 3, 5-difluorophenylalanine of 20mmol/L, which is recorded as ZnSO 4 +20mM 3,5-DDL。
Comparative example 1
The comparative example provides an electrolyte, a preparation method and application thereof, and the electrolyte comprises the following steps:
weigh 2.88g of solid ZnSO 4 ·7H 2 Adding O into 3.68ml deionized water, stirring thoroughly to obtain zinc sulfate solution with concentration of 2mol/L, and recording as ZnSO 4 。
Fig. 1 shows the contact angles of the electrolytes obtained in example 2 and comparative example 1 on commercial zinc foil substrates, the contact angle of the zinc sulfate electrolyte of comparative example 1 containing no additive at 2mol/L on the surface of the zinc foil is 99.02 °, and the contact angle of the modified electrolyte of example 2 with a concentration of 10mmol/L of difluoromethylornithine on the surface of the zinc foil is 85.59 °, indicating that the addition of difluoromethylornithine is advantageous for the improvement of the wettability of the electrolyte, which is advantageous for the ion transfer of the interface reaction.
The contact angle test results of examples 2-9 show that the addition of the water-soluble fluoroamino acid increases the wettability of the electrolyte.
Application example 1
Preparing a Zn symmetric battery: the commercial CR2025 electrode housing was used, with both positive and negative electrodes being commercial zinc foil (11 mm diameter) and the separator being a glass fiber separator (19 mm diameter). And (3) dripping 150 mu L of the modified electrolyte obtained in the embodiment 1 on a diaphragm, assembling the battery according to the sequence of the positive electrode shell, the zinc foil, the diaphragm, the electrolyte, the zinc foil, the elastic sheet, the gasket and the negative electrode shell, and pressurizing and packaging after the assembly is completed to prepare the Zn symmetric battery.
Preparing a Zn I Cu half cell: the commercial CR2025 electrode was used with a commercial copper foil (11 mm diameter) as the positive electrode and a commercial zinc foil (11 mm diameter) as the negative electrode, and a glass fiber separator (19 mm diameter) was used as the separator. And (3) dripping 150 mu L of the modified electrolyte obtained in the embodiment 1 on a diaphragm, assembling the battery according to the sequence of the positive electrode shell, the copper foil, the diaphragm, the electrolyte, the zinc foil, the elastic sheet, the gasket and the negative electrode shell, and pressurizing and packaging after the assembly is completed to prepare the Zn Cu half battery.
Preparing a Zn NVO full battery: using a commercial CR2025 type electrode housing, the positive electrode was carbon paper coated with sodium vanadate (11 mm diameter), the negative electrode was commercial zinc foil (11 mm diameter), and the separator was a glass fiber separator (19 mm diameter). And (3) dripping 150 mu L of the modified electrolyte obtained in the embodiment 1 on a diaphragm, assembling the battery according to the sequence of a positive electrode shell, a positive electrode, the diaphragm, an electrolyte, a zinc foil, an elastic sheet, a gasket and a negative electrode shell, and pressurizing and packaging after the assembly is completed to prepare the Zn NVO full battery.
Application example 2
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 2, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 2, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 2, and the other conditions were the same as in application example 1.
Application example 3
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 3, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 3, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 3, and the other conditions were the same as in application example 1.
Application example 4
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 4, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 4, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 4, and the other conditions were the same as in application example 1.
Application example 5
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 5, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 5, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 5, and the other conditions were the same as in application example 1.
Application example 6
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 6, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 6, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 6, and the other conditions were the same as in application example 1.
Application example 7
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 7, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 7, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 7, and the other conditions were the same as in application example 1.
Application example 8
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 8, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 8, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 8, and the other conditions were the same as in application example 1.
Application example 9
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 9, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 9, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in example 9, and the other conditions were the same as in application example 1.
Comparative application example 1
Preparing a Zn symmetric battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in comparative example 1, and the other conditions were the same as in application example 1.
Preparing a Zn I Cu half cell: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in comparative example 1, and the other conditions were the same as in application example 1.
Preparing a Zn NVO full battery: 150. Mu.L of the modified electrolyte obtained in example 1 was replaced with 150. Mu.L of the modified electrolyte obtained in comparative example 1, and the other conditions were the same as in application example 1.
The electrochemical performance of the prepared water-based zinc ion battery is tested by using a LAND CT2001A tester (blue electric Limited of Wuhan City).
Constant-current charge and discharge tests are carried out on Zn symmetric batteries at 30 ℃, and the current density is 0.25mAcm -2 ～5mA cm -2 The surface capacity is 0.25mAh cm -2 ～1mAh cm -2 。
Constant-current charge and discharge test is carried out on the Zn-Cu half cell at 30 ℃, and the current density is 0.25mA cm -2 ～5mA cm -2 The surface capacity is 0.25mAh cm -2 ～1mAh cm -2 The cut-off voltage was 0.5V.
The Zn NVO full cell is subjected to charge and discharge test at 30 ℃ and has a current density of 0.1Ag -1 ～5Ag -1 。
FIG. 2 shows that the Zn symmetric batteries obtained by assembling application example 2 and comparative application example 1 had a current density of 5mAcm -2 The surface capacity is 1mAh cm -2 Cycling performance graph under conditions. Under the above test conditions, the cycle life of the symmetrical battery assembled by comparative application example 1 using 2mol/L zinc sulfate electrolyte was only 190 hours, while the symmetrical battery assembled by application example 2 using modified electrolyte having a concentration of difluoromethylornithine of 10mmol/L was stably circulated 1954 hours, resulting in a 9-fold improvement in the cycle life of the zinc anode, whichThe presence of the additive greatly improves the long-cycle stability of the zinc anode.
Fig. 3 is an XPS diagram of the surface of a zinc anode after cycling of Zn symmetric batteries obtained in application example 2 and comparative application example 1. At a current density of 1mAcm -2 The surface capacity is 1mAh cm -2 After 50 weeks of circulation under the condition, the Zn 2P signal on the surface of the zinc cathode of the symmetrical battery assembled by using 2mol/L zinc sulfate electrolyte only has two characteristic peaks of Zn at 1044eV and 1021 eV; whereas after symmetric cell cycling assembled with modified electrolyte having a difluoromethylornithine concentration of 10mmol/L, broadening of the characteristic peak of Zn 2P signal typical for the zinc anode surface was attributed to the formation of Zn-F bonds, and the appearance of two new peaks, 1046eV and 1023eV, indicated that the zinc anode surface was ZnF 2 And (6) generating a layer.
Fig. 4 is an SEM image of the surface of the zinc anode after cycling of the Zn symmetric battery assembled in application example 2 and comparative application example 1. At a current density of 1mA cm -2 The surface capacity is 1mAh cm -2 After 50 weeks of circulation under the test conditions of (2) mol/L zinc sulfate electrolyte, the surface of the zinc cathode of the symmetrical battery assembled by the zinc sulfate electrolyte presents a surface with obvious roughness, and a large amount of zinc dendrites can be observed to show that Zn 2 Is deposited irregularly; and after the symmetrical battery assembled by using the modified electrolyte with the difluoromethylornithine concentration of 10mmol/L is circulated, the surface of the zinc cathode is flat and uniform, and obvious dendrites are not generated, so that the difluoromethylornithine effectively inhibits the formation of zinc dendrites.
Fig. 5 is a graph of the full battery rate performance of zn||nvo assembled by application example 2 and comparative application example 1. As shown in the figure, the Zn NVO full cells of application example 2 and comparative application example 1 were sequentially subjected to current densities of 0.1, 0.2, 0.5, 1, 2, 52A/g -1 And the discharge capacity of the battery is tested after 5 weeks of the next charge-discharge cycle, wherein the charge-discharge cut-off voltage range is 0.3V-1.5V. Full cells assembled with 2mol/L zinc sulfate electrolyte returned to 0.1A/g at current due to dissolution of NVO positive electrode material -1 When the specific capacity is rapidly attenuated, the formation of CEI film on the surface of the positive electrode material inhibits the dissolution of NVO positive electrode material, and the current returns to 0.1A/g when the current is returned to the full battery assembled by using the modified electrolyte with the concentration of difluoromethylornithine of 10mmol/L -1 The specific capacity remains stable.
Fig. 6 is a graph showing the cycle performance of the Zn NVO full cell obtained by assembling application example 2 and comparative application example 1. As shown in the figure, at 2A/g -1 The specific capacity of a full cell assembled with 2mol/L zinc sulfate electrolyte gradually decreases in 2500 weeks of charge-discharge cycles; and in the whole battery assembled by using the modified electrolyte with the difluoromethylornithine concentration of 10mmol/L, the specific capacity of the battery is slowly reduced in the whole charge-discharge cycle, and the capacity retention rate is 71% after 2500 weeks of cycle, which indicates that the difluoromethylornithine additive can effectively improve the stability of the NVO positive electrode material, thereby improving the cycle stability of the whole battery.
The zinc ion batteries obtained by the assembly of the application examples 1-9 and the comparative application example 1 are subjected to electrochemical performance test, wherein the Zn symmetric battery has a current density of 5mAcm -2 The surface capacity is 1mAh cm -2 Is circulated under the condition of (2); the Zn NVO full battery is subjected to charge and discharge test at 30 ℃, and the charge and discharge cut-off voltage range is 0.3V-1.5V, and the current density is 2A g -1 The test results are shown in Table 1.
TABLE 1
From the results, the fluoro amino acid additive of the invention can be adsorbed on the surface of the zinc cathode, and Zn is regulated and controlled 2+ Deposition behavior during charge and discharge, inhibiting Zn 2+ To inhibit dendrite growth; the fluoro amino acid additive can improve Zn 2+ Changing Zn in coordination environment 2+ Is solvated to reduce Zn 2+ The water molecule content in the complex can inhibit side reaction. In addition, the introduction of the fluoro amino acid additive can form an outer organic matter enrichment inner F inorganic matter enrichment CEI layer on the surface of the positive electrode material, and can inhibit transitionAnd metal ions are dissolved out, so that the stability of the positive electrode material is improved. Therefore, the fluoro amino acid additive is used as the electrolyte additive of the zinc ion battery, and the cycle life of the zinc ion battery can be obviously prolonged. The fluoro amino acid additive effectively solves the problems of generation of microcracks of positive electrode material particles, dissolution of transition metal ions and corrosion of zinc dendrites and zinc, has the advantages of simple preparation process, high safety, environmental friendliness and the like, and has wide application prospect in the field of water-based zinc ion batteries.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (10)
1. An electrolyte additive for an aqueous zinc ion battery, characterized by: the electrolyte additive is water-soluble fluorinated amino acid, and the current density of the water-based zinc ion battery is 5-10 mA cm -2 The positive electrode material of the water-based zinc ion battery is a transition metal-based positive electrode material.
2. An electrolyte additive for an aqueous zinc-ion battery according to claim 1, wherein: the water-soluble fluoro amino acid is difluoromethylornithine, 3-fluoroalanine or 3, 5-difluorophenylalanine.
3. An electrolyte for an aqueous zinc ion battery, characterized in that: the electrolyte comprises soluble zinc salt and H 2 O, additive according to claim 1 or 2.
4. An electrolyte for an aqueous zinc-ion battery according to claim 3, wherein: in the electrolyte, the soluble zinc salt is more than one of zinc sulfate, zinc sulfate hydrate, zinc chloride and hydrate thereof, zinc trifluoromethane sulfonate and hydrate thereof.
5. An electrolyte for an aqueous zinc-ion battery according to claim 4, wherein: in the electrolyte, the molar concentration of the soluble zinc salt is 1-3 mol/L; the molar concentration of the additive is 1-20 mmol/L.
6. An electrolyte for an aqueous zinc-ion battery according to claim 5, wherein: in the electrolyte, the molar concentration of the additive is 8-12 mmol/L.
7. An electrolyte for an aqueous zinc-ion battery according to claim 3, wherein: the electrolyte also comprises a manganese ion additive.
8. An electrolyte for an aqueous zinc-ion battery according to claim 7, wherein: the manganese ion additive is one or more of manganese nitrate, manganese sulfate and manganese chloride; the molar concentration of the manganese ion additive is 0.05mol/L to 0.5mol/L.
9. A water-based zinc ion battery, characterized in that: comprising the electrolyte according to any one of claims 3 to 8, a transition metal-based positive electrode material, a negative electrode material, and a separator.
10. A water-based zinc-ion battery according to claim 9, wherein: the negative electrode material comprises zinc sheets, zinc foils, zinc powder and foam zinc;
the positive electrode material is lithium manganate, manganese dioxide, vanadium pentoxide or sodium vanadate;
the diaphragm is glass fiber.
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