CN114122533A - Multifunctional composite electrolyte of neutral or weak acid zinc-based battery - Google Patents
Multifunctional composite electrolyte of neutral or weak acid zinc-based battery Download PDFInfo
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- CN114122533A CN114122533A CN202010883598.9A CN202010883598A CN114122533A CN 114122533 A CN114122533 A CN 114122533A CN 202010883598 A CN202010883598 A CN 202010883598A CN 114122533 A CN114122533 A CN 114122533A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003792 electrolyte Substances 0.000 title claims abstract description 64
- 239000011701 zinc Substances 0.000 title claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 230000007935 neutral effect Effects 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 title abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 50
- 238000005260 corrosion Methods 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 239000003607 modifier Substances 0.000 claims abstract description 33
- 210000001787 dendrite Anatomy 0.000 claims abstract description 32
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 229920000620 organic polymer Polymers 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 6
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000176 sodium gluconate Substances 0.000 claims description 6
- 235000012207 sodium gluconate Nutrition 0.000 claims description 6
- 229940005574 sodium gluconate Drugs 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- -1 aluminum ions Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- QNDGQRJVVZJMJO-UHFFFAOYSA-N 2-(2-undecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCC1=NCCN1CCO QNDGQRJVVZJMJO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 3
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 3
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- HMJWAKCBJWAMPL-UHFFFAOYSA-M triethyl(phenyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)C1=CC=CC=C1 HMJWAKCBJWAMPL-UHFFFAOYSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-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 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 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
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 150000008043 acidic salts Chemical class 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 125000002636 imidazolinyl group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000009422 growth inhibiting effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous 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)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention relates to a multifunctional composite electrolyte of a neutral or weak acid zinc-based battery, which comprises the following components in part by weight: solvents, solutes, and multifunctional modifiers; the solvent is selected from zinc salts; the multifunctional modifier is at least 3 selected from surfactant, organic polymer solubilizer, quaternary ammonium salt dendrite resisting agent, imidazolyl corrosion inhibitor and zinc ion complexing agent.
Description
Technical Field
The invention relates to an electrolyte for a zinc battery, in particular to a multifunctional composite electrolyte for a neutral or weakly acidic zinc-based battery, belonging to the technical field of zinc battery electrolytes.
Background
The zinc-based water system battery has the characteristics of low cost, high energy density, good safety and the like, and has wide application prospect in the fields of large-scale energy storage and portability. The zinc-based water system battery adopts weak acid (pH is between 3 and 7) salt solution as electrolyte, metal zinc with high specific energy as a negative electrode, and an ion deintercalation compound with high stability as a positive electrode. In the process of the cyclic charge and discharge of the battery, the dissolution and deposition reaction of zinc ions occurs on the negative electrode side of zinc, the embedding and removing reaction of ions occurs on the positive electrode side, and the electrolyte plays a role in ion transmission. The electrode potential of the metal zinc is-0.76V, the chemical activity is high, the metal zinc is unstable in a weak acid salt solution, corrosion reaction is easy to occur and loss is caused, the capacity of the battery is attenuated, and the performance of the battery is reduced. Meanwhile, during the cyclic charge and discharge process of the battery, zinc ions are unevenly dissolved and deposited to cause the growth of zinc dendrites, the zinc dendrites are broken and dissolved to cause the generation of dead zinc, the zinc cathode is continuously lost, and the cycle life of the battery is shortened; when the zinc dendrites pierce the diaphragm, the internal short circuit of the battery can be caused, and the battery is scrapped.
According to the invention of chinese patent document 1 (publication No. CN109273759A), in order to solve the problems of corrosion of the zinc negative electrode and growth of dendrite, the present invention replaces the aqueous solvent with an ether solvent, and although the problems of corrosion of the zinc negative electrode and growth of dendrite can be alleviated, the use of an organic solvent significantly reduces the ionic conductivity of the electrolyte, and the cost is relatively high.
According to the chinese invention patent document 2 (publication No. CN110828896A), the invention discloses the use of a multifunctional modifier for suppressing metal dendrites, an electrolyte and a battery containing the multifunctional modifier, which have the effect of effectively suppressing the growth of metal dendrites, but do not mention the corrosion suppressing effect of the multifunctional modifier.
According to chinese invention patent document 3 (publication No. CN108807910A), the present invention provides an aqueous zinc ion battery in which a small amount of manganese salt and a corrosion inhibitor are added to an electrolyte solution, and the problems of zinc corrosion, passivation, and the like can be effectively alleviated. However, the dendritic growth inhibiting effect of the multifunctional modifier is not mentioned.
In the above patent, the zinc-based aqueous battery can only solve some technical problems of the zinc-based aqueous battery, but the problems of corrosion, dendrite growth, and the like in the zinc-based aqueous battery cannot be considered from a multi-functional and all-round point of view in addition to the aqueous electrolyte.
Disclosure of Invention
In order to overcome the technical defects, the invention aims to provide a multifunctional composite electrolyte for a zinc-based aqueous battery, which comprises the following components: solvents, solutes, and multifunctional modifiers; the solvent is selected from zinc salts; the multifunctional modifier is at least 3 selected from surfactant, organic polymer solubilizer, quaternary ammonium salt dendrite resisting agent, imidazolyl corrosion inhibitor and zinc ion complexing agent.
In the invention, the composite electrolyte containing at least 3 decorative agents can effectively relieve the corrosion problem (based on the surfactant, the organic polymer solubilizer and the imidazole anticorrosive agent) of the zinc electrode in the aqueous electrolyte and can effectively inhibit the zinc dendrite growth problem (based on the surfactant, the organic polymer solubilizer and the quaternary ammonium cation) of the battery in the cyclic charge-discharge process, thereby improving the cycle stability and the cycle life of the zinc-based aqueous battery.
Preferably, the solvent is water.
Preferably, the zinc salt is at least one selected from zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc nitrate, zinc chloride and zinc perchlorate; preferably, the solute further comprises other metal salts, and cations of the other metal salts are selected from at least one of potassium ions, sodium ions, lithium ions, manganese ions, calcium ions, magnesium ions and aluminum ions.
Preferably, the other metal salt is at least one selected from the group consisting of trifluoromethanesulfonate, sulfate, acetate, nitrate, chloride and perchlorate.
Preferably, the concentration of the zinc salt is 0.1-3 moL/L; the concentration of the other metal salts is 0.1-1 moL/L.
Preferably, the surfactant is selected from at least one of tween-20, tween-80, surfynol 104E, OP- (4, 6, 7, 9, 10), NP- (4, 6, 7, 9, 10); wherein OP is octylphenol polyoxyethylene ether, NP is nonylphenol polyoxyethylene ether, and the number represents the number of ethylene oxide segments added in the molecular structure;
the organic polymer solubilizer is selected from at least one of starch, carboxymethyl cellulose, carboxyethyl cellulose and sodium polyacrylate (the solubilizer mainly improves the solubility of various functional additives and promotes the stability and compatibility of the solution);
the quaternary ammonium salt dendrite resisting agent is at least one of dodecyl dimethyl benzyl ammonium bromide, benzyl triethyl ammonium bromide, benzyl trimethyl ammonium bromide and phenyl triethyl ammonium bromide;
the imidazole-based anticorrosive is selected from at least one of imidazoline, lauryl hydroxyethyl imidazoline and benzimidazole (mainly improves the corrosion resistance of the zinc electrode to the electrolyte);
the zinc ion complexing agent is at least one selected from sodium hexametaphosphate, sodium gluconate, sodium tartrate and sodium alginate.
In the invention, on the basis of a neutral or weakly acidic salt solution, a multifunctional modifier with different types and functions is introduced, so that the corrosion problem of the zinc cathode in the weakly acidic salt solution and the dendritic crystal growth problem of the zinc cathode in the cyclic charge-discharge process can be effectively relieved. Active substances such as a surfactant, an organic polymer solubilizer, an imidazole anticorrosive agent and the like in the multifunctional modifier can be adsorbed on the surface of zinc metal, so that corrosion sites exposed on the surface of zinc in electrolyte are reduced, and the corrosion influence of a zinc electrode in the electrolyte is reduced. In the cyclic charge and discharge process, when zinc ions deposit on the zinc negative electrode side, active substances such as a surfactant, an organic polymer solubilizer, quaternary ammonium salt cations and the like in the multifunctional modifier can be preferentially adsorbed in high-activity and high-current-density areas such as surface defects, protrusions and dendritic crystals of the zinc negative electrode, so that zinc ion flow can be restrained, zinc deposition can be normalized, and the growth of zinc dendritic crystals can be restrained. The surfactant, the organic polymer solubilizer and the zinc ion complexing agent in the multifunctional modifier can play a role in dispersing, so that the compatibility of various multifunctional modifiers is improved, and the generation of turbid substances is reduced.
Preferably, the total dosage of the multifunctional modifier is 0.01wt% -5 wt%.
The addition amount of the surfactant in the electrolyte can be 0-5 wt%, preferably 0.01-0.5 wt%;
the addition amount of the organic polymer solubilizer in the electrolyte can be 0-1 wt%, preferably 0.01-0.5 wt%;
the addition amount of the quaternary ammonium salt dendrite resisting agent in the electrolyte can be 0-0.1 wt%, and preferably 0.01-0.05 wt%;
the addition amount of the imidazolyl corrosion inhibitor in the electrolyte can be 0-0.5 wt%, preferably 0.02-0.1 wt%;
the addition amount of the zinc ion complexing agent in the electrolyte can be 0-0.5 wt%, and preferably 0.01-0.1 wt%.
Preferably, the pH value of the electrolyte is 3-7.
On the other hand, the invention also provides a symmetrical battery containing the multifunctional composite electrolyte.
Has the advantages that:
the corrosion of the zinc cathode of the water-based battery with the multifunctional composite electrolyte in a weakly acidic salt solution is relieved, the loss of the zinc cathode side is reduced, and the coulomb efficiency of the zinc cathode is improved. Meanwhile, dendritic crystal growth of the zinc cathode in the cyclic charge and discharge process of the battery is relieved, and the cyclic stability and the cyclic service life of the battery are improved. The preparation method of the electrolyte is simple, and the multifunctional modifier components can compatibly and synergistically play the functions of corrosion inhibition, dendrite inhibition and the like, thereby being beneficial to the application development of the zinc-based water-based battery.
Drawings
FIG. 1 is a cycle diagram of a comparative example 1 symmetrical cell of the present invention;
FIG. 2 is a cycle diagram of a comparative example 2 symmetrical cell of the present invention;
FIG. 3 is a cycle diagram of a comparative example 3 symmetrical cell of the present invention;
FIG. 4 is a cycle diagram of a comparative example 4 symmetrical cell of the present invention;
FIG. 5 is a cycle diagram of a symmetrical battery of example 1 of the present invention;
fig. 6 is a cycle diagram of a symmetrical battery of example 2 of the present invention;
fig. 7 is a cycle diagram of a symmetric cell of example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present invention, there is provided a multifunctional composite electrolyte suitable for a neutral or weakly acidic zinc-based battery, which includes a plurality of types of electrolyte modifiers (e.g., at least 3, preferably at least 4, and most preferably a surfactant, a quaternary ammonium salt anti-dendrite agent, an imidazolyl corrosion inhibitor, and a zinc ion complexing agent) in addition to a solvent (water) and a solute (zinc salt). The introduction of the multi-type electrolyte modifier can play a synergistic effect, so that the dispersion and dissolution of neutral or weakly acidic zinc ion electrolyte can be effectively improved, the corrosion of a zinc-based metal or alloy electrode in aqueous electrolyte is inhibited, the problem of zinc dendrite growth in the process of cyclic charge and discharge of a battery can be prevented, the loss of a zinc cathode is reduced, the growth of zinc dendrite is inhibited, and the cyclic stability and the cyclic service life of the zinc-based aqueous battery are improved.
In alternative embodiments, the multifunctional modifying agents can be classified by structure and type of action as 1) surfactants (Tween-20, Tween-80, surfynol 104E, OP- (4, 6, 7, 9, 10), NP- (4, 6, 7, 9, 10), etc.); 2) organic polymer solubilizers (starch, carboxymethyl cellulose, carboxyethyl cellulose, sodium polyacrylate, etc.); 3) quaternary ammonium salt dendrite inhibitors (dodecyl dimethyl benzyl ammonium bromide, benzyl triethyl ammonium bromide, benzyl trimethyl ammonium bromide, phenyl triethyl ammonium bromide, etc.); 4) imidazolyl corrosion inhibitors (imidazoline, lauryl hydroxyethyl imidazoline, benzimidazole); 5) zinc ion complexing agent (sodium hexametaphosphate, sodium gluconate, sodium tartrate, sodium alginate, etc.) including three or more of the above. Preferably, the total dosage of the multifunctional modifier accounts for 0.01wt% -5 wt% of the total mass of the electrolyte.
Wherein, the addition amount of the surfactant in the electrolyte can be 0-5 wt%, preferably 0.01-0.5 wt%.
Wherein, the addition amount of the organic polymer solubilizer in the electrolyte can be 0-1 wt%, preferably 0.01-0.5 wt%.
Wherein, the addition amount of the quaternary ammonium salt dendrite resisting agent in the electrolyte can be 0-0.1 wt%, and preferably 0.01-0.05 wt%.
The addition amount of the imidazolyl corrosion inhibitor in the electrolyte can be 0-0.5 wt%, preferably 0.02-0.1 wt%.
The addition amount of the zinc ion complexing agent in the electrolyte can be 0-0.5 wt%, and preferably 0.01-0.1 wt%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The corrosion inhibition effect of the multifunctional modifier is tested by an electrochemical method. The corrosion rate of the metal zinc electrode in neutral/weak acidic salt solution can be represented by corrosion current density, the corrosion inhibition effect of the multifunctional modifier can be represented by corrosion inhibition rate, and the calculation formula of the corrosion inhibition rate eta is as follows:
η＝(J0-J)/J0；
j in the formula0Is the corrosion current density of the metal zinc electrode in the solution of the control group; j is the corrosion current density of the zinc metal electrode in the solution containing the multifunctional modifier.
In the testing process, a metal zinc foil is used as a metal zinc electrode, the working surface of the metal zinc electrode is firstly polished by metallographic abrasive paper, then the dirt on the metal surface is completely removed by deionized water and ethanol, the zinc electrode is wiped by non-woven paper, the working area of the metal zinc electrode is placed into a testing solution for 5-10 minutes, an electrochemical workstation is used for testing the corrosion potential and the corrosion current density of the metal zinc electrode at room temperature, the corrosion inhibition rate is calculated, and comparative analysis is carried out.
The invention adopts a symmetrical battery with high discharge depth to circularly test the dendritic crystal inhibition effect of the multifunctional modifier. The dendrite inhibiting effect of the metallic zinc cathode can be expressed by the cycle time of a symmetrical battery, and the longer the cycle time of the symmetrical battery is, the better the dendrite growth inhibiting effect is.
The following examples were all conducted under the above test conditions.
Example 1
A multifunctional composite electrolyte of zinc-base water-system battery is composed of solvent, solute and multifunctional modifier. The solvent is water, the solute is zinc sulfate, and 1mol/L ZnSO is prepared4And (3) solution. The multifunctional modifier comprises a surfactant, an organic polymer solubilizer, a quaternary ammonium salt dendrite-resistant agent, an imidazolyl corrosion inhibitor and a zinc ion complexing agent.
The surfactant is surfynol 104E, and the mass concentration is 0.05%. The organic polymer solubilizer is carboxymethyl cellulose, and the mass concentration of the carboxymethyl cellulose is 0.05%. The quaternary ammonium salt dendrite resisting agent is benzyl triethyl ammonium bromide, and the mass concentration of the quaternary ammonium salt dendrite resisting agent is 0.02%. The imidazolyl corrosion inhibitor is imidazoline, and the mass concentration of the imidazolyl corrosion inhibitor is 0.02%. The zinc ion complexing agent is sodium gluconate with the mass concentration of 0.05%.
Example 2
A multifunctional composite electrolyte of zinc-base water-system battery is composed of solvent, solute and multifunctional modifier. The solvent is water, the solute is zinc sulfate, and 1mol/L ZnSO is prepared4And (3) solution. The multifunctional modifier comprises a surfactant, an organic polymer solubilizer, a quaternary ammonium salt dendrite-resistant agent, an imidazolyl corrosion inhibitor and a zinc ion complexing agent.
The surfactant is OP-10 and surfynol 104E, the mass concentration of the OP-10 is 0.05 percent, and the mass concentration of the surfynol 104E is 0.05 percent. The organic polymer solubilizer is carboxymethyl cellulose, and the mass concentration of the carboxymethyl cellulose is 0.05%. The quaternary ammonium salt dendrite resisting agent is benzyl triethyl ammonium bromide, and the mass concentration of the quaternary ammonium salt dendrite resisting agent is 0.02%. The imidazolyl corrosion inhibitor is imidazoline, and the mass concentration of the imidazolyl corrosion inhibitor is 0.05%. The zinc ion complexing agent is sodium gluconate with the mass concentration of 0.05%.
Example 3
A multifunctional composite electrolyte of zinc-base water-system battery is composed of solvent, solute and multifunctional modifier. The solvent is water, the solute is zinc sulfate, and 1mol/L ZnSO is prepared4And (3) solution. The multifunctional modifier comprises a surfactant, an organic polymer solubilizer, a quaternary ammonium salt dendrite-resistant agent, an imidazolyl corrosion inhibitor and a zinc ion complexing agent.
The surfactant is OP-10 and surfynol 104E, the mass concentration of the OP-10 is 0.05 percent, and the mass concentration of the surfynol 104E is 0.05 percent. The organic polymer solubilizer is carboxymethyl cellulose, and the mass concentration of the carboxymethyl cellulose is 0.05%. The quaternary ammonium salt dendrite resisting agent is benzyl triethyl ammonium bromide, and the mass concentration of the quaternary ammonium salt dendrite resisting agent is 0.03%. The imidazolyl corrosion inhibitor is imidazoline, and the mass concentration of the imidazolyl corrosion inhibitor is 0.05%. The zinc ion complexing agent is sodium gluconate with the mass concentration of 0.05%.
Comparative example 1
A multifunctional composite electrolyte for Zn-base water-system battery is composed of solvent and solute. The solvent is water, the solute is zinc sulfate, and 1mol/L ZnSO is prepared4Solution, without any multifunctional modifier added.
Comparative example 2
The electrolyte preparation process in this comparative example 2 was as described in example 1, except that: no imidazolyl corrosion inhibitors were added.
Comparative example 3
The electrolyte preparation process in this comparative example 3 was as described in example 1 except that: no quaternary ammonium salt anti-dendrite agent is added.
Comparative example 4
The electrolyte preparation process in this comparative example 4 was as described in example 1 except that: no surfactant, organic polymer solubilizer and zinc ion complexing agent are added.
Table 1 shows the corrosion current density, corrosion inhibition rate and symmetric cell cycle time for each test solution:
| corrosion current density/mA cm-2 | Inhibition rate/%) | Symmetric cell cycle time/h | |
| Comparative example 1 | 65.2×10-2 | 0 | 150 |
| Comparative example 2 | 7.55×10-2 | 88.4 | 179 |
| Comparative example 3 | 4.05×10-2 | 93.8 | 228 |
| Comparative example 4 | 6.30×10-2 | 90.3 | 198 |
| Example 1 | 3.91×10-2 | 94.0 | 329 |
| Example 2 | 3.44×10-2 | 94.7 | 345 |
| Example 3 | 3.37×10-2 | 94.8 | 396 |
As shown in Table 1, compared with the electrolyte without the multifunctional modifier in the comparative example 1, the multifunctional composite electrolyte has lower corrosion current, higher corrosion inhibition rate and longer symmetrical battery cycle time on the zinc cathode, and the multifunctional composite electrolyte has the advantages of good corrosion inhibition effect on the zinc cathode in a weakly acidic salt solution, good dendritic crystal growth inhibition effect and capability of obviously prolonging the cycle life of the battery.
The above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and the insubstantial modifications and adaptations made by those skilled in the art based on the above descriptions of the present invention are within the scope of the present invention.
Claims (10)
1. A multifunctional composite electrolyte for a neutral or weakly acidic zinc-based battery, the multifunctional composite electrolyte comprising: solvents, solutes, and multifunctional modifiers; the solvent is selected from zinc salts; the multifunctional modifier is at least 3 selected from surfactant, organic polymer solubilizer, quaternary ammonium salt dendrite resisting agent, imidazolyl corrosion inhibitor and zinc ion complexing agent.
2. The multifunctional composite electrolyte according to claim 1, wherein the solvent is water.
3. The multifunctional composite electrolyte according to claim 1 or 2, wherein the zinc salt is selected from at least one of zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc nitrate, zinc chloride and zinc perchlorate;
preferably, the solute further comprises other metal salts, and cations of the other metal salts are selected from at least one of potassium ions, sodium ions, lithium ions, manganese ions, calcium ions, magnesium ions and aluminum ions.
4. The multifunctional composite electrolyte according to claim 3, wherein the other metal salt is at least one selected from the group consisting of triflate, sulfate, acetate, nitrate, chloride, and perchlorate.
5. The multifunctional composite electrolyte according to any one of claims 1 to 4, wherein the concentration of the zinc salt is 0.1 to 3 moL/L; the concentration of the other metal salts is 0.1-1 moL/L.
6. The multifunctional composite electrolyte according to any one of claims 1 to 5, wherein the surfactant is selected from at least one of Tween-20, Tween-80, surfynol 104E, OP- (4, 6, 7, 9, 10), NP- (4, 6, 7, 9, 10);
the organic polymer solubilizer is selected from at least one of starch, carboxymethyl cellulose, carboxyethyl cellulose and sodium polyacrylate;
the quaternary ammonium salt dendrite resisting agent is at least one of dodecyl dimethyl benzyl ammonium bromide, benzyl triethyl ammonium bromide, benzyl trimethyl ammonium bromide and phenyl triethyl ammonium bromide;
the imidazole-based anticorrosive is selected from at least one of imidazoline, lauryl hydroxyethyl imidazoline and benzimidazole;
the zinc ion complexing agent is at least one selected from sodium hexametaphosphate, sodium gluconate, sodium tartrate and sodium alginate.
7. The multifunctional composite electrolyte as claimed in any one of claims 1 to 6, wherein the multifunctional modifier is used in a total amount of 0.01 to 5 wt%.
8. The multifunctional composite electrolyte of claim 7, wherein the surfactant is added in the electrolyte in an amount of 0 to 5wt%, preferably 0.01 to 0.5 wt%;
the addition amount of the organic polymer solubilizer in the electrolyte is 0-1 wt%, preferably 0.01-0.5 wt%;
the addition amount of the quaternary ammonium salt dendrite resisting agent in the electrolyte is 0-0.1 wt%, preferably 0.01-0.05 wt%;
the addition amount of the imidazolyl corrosion inhibitor in the electrolyte is 0-0.5 wt%, preferably 0.02-0.1 wt%;
the addition amount of the zinc ion complexing agent in the electrolyte is 0-0.5 wt%, preferably 0.01-0.1 wt%.
9. The multifunctional composite electrolyte according to any one of claims 1 to 8, wherein the pH of the electrolyte is 3 to 7.
10. A symmetrical battery comprising the multifunctional composite electrolyte of any one of claims 1-9.
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| US20180316064A1 (en) * | 2015-10-21 | 2018-11-01 | Research Foundation Of The City University Of New New York | Additive for Increasing Lifespan of Rechargeable Zinc-Anode Batteries |
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| CN102054994A (en) * | 2010-12-10 | 2011-05-11 | 株洲江海环保实业有限公司 | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof |
| US20180316064A1 (en) * | 2015-10-21 | 2018-11-01 | Research Foundation Of The City University Of New New York | Additive for Increasing Lifespan of Rechargeable Zinc-Anode Batteries |
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