CN111384424B - Lignin-based composite electrolyte for aqueous zinc-ion batteries and aqueous zinc-ion batteries based thereon - Google Patents
Lignin-based composite electrolyte for aqueous zinc-ion batteries and aqueous zinc-ion batteries based thereon Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 159
- 229920005610 lignin Polymers 0.000 title claims abstract description 140
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229920001732 Lignosulfonate Polymers 0.000 claims description 21
- 235000019357 lignosulphonate Nutrition 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 238000004880 explosion Methods 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- HEYNLDRKZOOEDN-UHFFFAOYSA-L manganese(2+);trifluoromethanesulfonate Chemical compound [Mn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HEYNLDRKZOOEDN-UHFFFAOYSA-L 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 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 7
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 238000007385 chemical modification Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 44
- 229910052725 zinc Inorganic materials 0.000 abstract description 44
- 210000001787 dendrite Anatomy 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 8
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- -1 manganese salt Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 42
- 239000007864 aqueous solution Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 150000001412 amines Chemical group 0.000 description 10
- 230000002401 inhibitory effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002255 enzymatic effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229920005550 ammonium lignosulfonate Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 102000008109 Mixed Function Oxygenases Human genes 0.000 description 1
- 108010074633 Mixed Function Oxygenases Proteins 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明属于水系锌离子电池领域，公开了一种用于水系锌离子电池的木质素基复配型电解液和基于其的水系锌离子电池。该木质素基复配型电解液包括以下重量份数的组分：改性木质素100份；水相电解液(水溶性锌盐和水溶性锰盐的混合溶液)150～100000份。本发明木质素基复配型电解液应用于水系锌离子电池，可一定程度抑制正极的副反应，降低锌负极腐蚀，并同时调控充放电过程中锌离子在锌负极表面均匀地溶出和沉积，以抑制锌枝晶的形成和生长，从而大幅提升水系锌离子电池的倍率和循环性能。此外，本发明提供的木质素来源广泛、可再生且价格低廉，有助于开发绿色环保、性能优异且成本低的水系锌离子电池，助力未来大规模储能系统的顺利实施。
The invention belongs to the field of aqueous zinc ion batteries, and discloses a lignin-based composite electrolyte for aqueous zinc ion batteries and an aqueous zinc ion battery based thereon. The lignin-based composite electrolyte includes the following components in parts by weight: 100 parts of modified lignin; and 150 to 100,000 parts of an aqueous electrolyte (a mixed solution of water-soluble zinc salt and water-soluble manganese salt). The lignin-based composite electrolyte of the present invention is applied to an aqueous zinc ion battery, which can suppress the side reaction of the positive electrode to a certain extent, reduce the corrosion of the zinc negative electrode, and at the same time regulate the uniform dissolution and deposition of the zinc ions on the surface of the zinc negative electrode during the charging and discharging process. In order to inhibit the formation and growth of zinc dendrites, the rate and cycle performance of aqueous zinc-ion batteries can be greatly improved. In addition, the lignin provided by the present invention has a wide range of sources, is renewable, and is inexpensive, which is helpful for the development of a water-based zinc-ion battery with environmental protection, excellent performance and low cost, and facilitates the smooth implementation of a large-scale energy storage system in the future.
Description
Technical Field
The invention belongs to the field of water-system zinc ion batteries, and particularly relates to a lignin-based compound electrolyte for a water-system zinc ion battery and a water-system zinc ion battery based on the lignin-based compound electrolyte.
Background
Currently, the development of a large energy storage system (LSESS) with high energy density, long service life, safety, low cost and environmental friendliness is an important direction for realizing sustainable development of human society. Water-based batteries are most promising for the establishment of LSESS due to their high electrolyte safety and low manufacturing cost. However, commercial water-based batteries, such as lead-acid batteries, nickel-chromium batteries, nickel-metal hydride batteries, and the like, all risk heavy metal contamination and corrosion damage due to leakage, while these batteries have low energy density and short cycle life. Therefore, development of a novel aqueous battery is of great significance for successful utilization of green and renewable energy. Among many water-based batteries, a rechargeable water-based zinc ion battery (reazob) with high capacity and energy density is most promising to be commercialized, but the problems of corrosion of a zinc negative electrode, zinc dendrite growth and the like are also required to be solved so as to further improve the rate performance, cycle life, stability and the like.
Zhang et al (Nature Communications,2017,8:405.) found Zn (CF)3SO3)2With a small amount of Mn (CF)3SO3)2The mixed aqueous solution is used as electrolyte, and can effectively inhibit the formation of zinc dendrites, thereby greatly improving the cycle performance of the ReAZIB, but the electrolyte is too expensive; zhang et al (Journal of Materials Chemistry A,2018,6(26):12237-4With a small amount of MnSO4The xanthan gum is added into the mixed aqueous solution, and the obtained colloidal electrolyte can reduce the corrosion of a zinc cathode to a certain degree and inhibit the growth of zinc dendrites, but can cause the over-quick loss of the initial capacity of the ReAZIB; some other scholars use nano CaCO3(Advanced Energy Materials,2018,8(25):1801090.) or nano TiO2(Advanced Materials Interfaces,2018,5(16):1800848.) coating on the surface of the zinc negative electrode can reduce the corrosion of the zinc negative electrode and inhibit the growth of zinc dendrites, but the adopted complex coating technology tends to greatly increase the manufacturing cost and difficulty of the ReAZIB. In contrast, the solution of the difficulties faced by ReAZIB through electrolyte additives has a great significance for the commercialization thereof, but the development of a high-performance and inexpensive electrolyte suitable for ReAZIB is being developedThe additive is heavy at random.
The industrial lignin is mainly derived from industrial wastes such as pulping and papermaking, cellulosic ethanol, wood hydrolysis and the like, the annual output is as high as 7000 ten thousand tons, but the utilization rate is less than 5 percent, and the rest of the industrial lignin is used as low-value fuel or directly discarded, so that huge resource waste and serious environmental pollution are caused. In recent years, the development and utilization of industrial lignin with high value have been receiving more and more extensive attention and research. It has been shown that lignosulfonate or sulfonated lignin can complex Pb2+And utilizes the three-dimensional network structure thereof to regulate and control PbSO4The crystal is uniformly deposited and dissolved out on the surface of the lead cathode, so that the capacity and the service life of the lead-acid battery are improved. This shows that the complexation of lignin derivatives to metal ions and their unique three-dimensional network structure can regulate the deposition and dissolution behavior of metal ions. Whereas in ReAZIB, zinc dendrites are formed primarily from Zn2+Uneven deposition and dissolution on the surface of the zinc cathode; it has been shown that the phenolic hydroxyl and carboxyl groups in lignin derivatives molecule are Zn2+Has good complexing effect, and the adsorption on the surface of the metal material can prevent the material from being corroded. Thus, lignin-based additives are expected to control Zn2+The zinc oxide is uniformly deposited and dissolved on the surface of the zinc cathode, the formation and growth of zinc dendrites are inhibited, the corrosion of the zinc cathode is reduced, and the electrochemical performance of the ReAZIB is improved, so that the method has important theoretical guidance significance for the high-valued application of lignin in a rechargeable aqueous battery.
Due to poor water solubility of alkali lignin, enzymatic lignin, organic solvent lignin and steam explosion lignin, negatively charged functional groups in lignosulfonate, sulfonated lignin and carboxylated lignin molecules are Zn-bonded2+Shielding, which makes them difficult to dissolve in aqueous zinc ion salt solutions. Therefore, it is first necessary to obtain a lignin-based complex electrolyte and an aqueous zinc ion battery using the same by introducing a hydroxyl group and an ammonium (amine) group into the lignin through a chemical modification reaction to ensure that the lignin is well dissolved in an aqueous electrolyte.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a lignin-based complex electrolyte for an aqueous zinc-ion battery.
Another object of the present invention is to provide an aqueous zinc-ion battery based on the lignin-based complex electrolyte.
The purpose of the invention is realized by the following scheme:
a lignin-based compound electrolyte for a water-based zinc ion battery is characterized by comprising the following components in parts by weight:
100 parts of modified lignin;
150-100000 parts of water-phase electrolyte.
The modified lignin comprises at least one of modified products which are obtained by taking lignosulfonate, sulfonated lignin, carboxylated lignin, alkali lignin, enzymatic hydrolysis lignin, organic solvent lignin and steam explosion lignin as main raw materials and grafting hydroxyl and ammonium (amine) functional groups into the modified lignin through chemical modification.
The modified lignin comprises at least one of hydroxylated lignin sulfonate, ammonium (amine) lignosulfonate, hydroxylated sulfonated lignin, ammonium (amine) sulfonated lignin, hydroxylated carboxylated lignin, ammonium (amine) carboxylated lignin, hydroxylated alkali lignin, ammonium (amine) basic lignin, hydroxylating enzyme-hydrolyzed lignin, ammonium (amine) enzymatic hydrolyzed lignin, hydroxylated organic solvent lignin, ammonium (amine) basic organic solvent lignin, hydroxylated steam explosion lignin and ammonium (amine) basic steam explosion lignin, and the dosage of each component can be any proportion.
The lignin-based compound electrolyte is prepared by mixing and stirring modified lignin and water-phase electrolyte until the modified lignin is fully dissolved.
The pH value of the lignin-based compound electrolyte is 2-7.
The pH value of the lignin-based compound electrolyte is preferably 3.5-6.
The water-phase electrolyte is formed by mixing water-soluble zinc salt and water-soluble manganese salt.
The water-soluble zinc salt comprises at least one of zinc sulfate, zinc chloride, zinc bromide, zinc iodide, zinc nitrate, zinc acetate and zinc trifluoromethanesulfonate; the water-soluble manganese salt comprises at least one of manganese sulfate, manganese chloride, manganese bromide, manganese iodide, manganese nitrate, manganese acetate and manganese trifluoromethanesulfonate; the water-soluble zinc salt and the water-soluble manganese salt can be matched at will.
The water-soluble zinc salt is preferably zinc sulfate and zinc trifluoromethanesulfonate; the water-soluble manganese salt is preferably manganese sulfate and manganese trifluoromethanesulfonate.
The concentration of the water-soluble zinc salt in the water-phase electrolyte is 0.1-15 mol/L, and the concentration of the water-soluble manganese salt is 0.01-2 mol/L.
The concentration of the water-soluble zinc salt is preferably 1-6 mol/L.
The invention also provides an aqueous zinc ion battery containing the lignin-based compound electrolyte.
The water system zinc ion battery comprises a battery shell, a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in the battery shell, the pole core comprises a positive pole capable of reacting with zinc ions, a zinc negative pole and a diaphragm positioned between the positive pole and the negative pole, and the electrolyte is lignin-based compound electrolyte as described above.
The mechanism of the invention is as follows:
according to the invention, the lignin-based compound electrolyte is applied to the water-based zinc ion battery, so that the rate capability and the cycle performance of the battery can be obviously improved. The modified lignin has hydroxyl and ammonium functional groups, and can provide Zn with strong hydrophilicity and no electropositivity2+Shielding to ensure that the electrolyte is well dissolved in the aqueous electrolyte; the benzene ring structure in the modified lignin can generate cation-pi interaction with the anode, so that a uniform lignin adsorption layer is formed on the surface of the anode, and side reactions in the anode are inhibited to a certain degree; hydroxyl and ammonium (amine) functional groups in the modified lignin can generate hydrogen bond interaction with the surface of the zinc cathode in aqueous electrolyte, so that a uniform lignin adsorption layer is formed on the surface of the zinc cathode, and the corrosion of the electrolyte to the zinc cathode can be inhibitedAnd the three-dimensional network structure of the modified lignin and the complexing effect on zinc ions can be utilized to regulate and control the zinc ions to be uniformly dissolved out and deposited on the surface of the zinc cathode in the charging and discharging processes of the battery so as to inhibit the formation and growth of zinc dendrites. Therefore, the lignin-based compound electrolyte can inhibit side reactions in the positive electrode and corrosion of the electrolyte to the zinc negative electrode to a certain extent, and can also significantly inhibit formation and growth of zinc dendrites, so that the rate capability and cycle performance of the water-based zinc ion battery are greatly improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the lignin-based compound electrolyte formed by compounding the modified lignin and the aqueous electrolyte in a proper proportion is applied to the water-based zinc ion battery, so that the side reaction in the positive electrode is inhibited to a certain extent, the corrosion of the electrolyte to the zinc negative electrode is reduced, and the formation and growth of zinc dendrites are obviously inhibited, so that the rate capability and the cycle performance of the water-based zinc ion battery are greatly improved, and the safety of the battery is also improved; on the other hand, the lignin provided by the invention is wide in source, renewable and low in price, and is beneficial to promoting the commercialization process of the water system zinc ion battery which is green, environment-friendly, excellent in performance and low in cost, and more suitable choices are provided for the future large-scale energy storage technology.
Drawings
Fig. 1(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of example 1, respectively.
Fig. 2(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of example 2, respectively.
Fig. 3(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of example 3, respectively.
Fig. 4(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of example 4, respectively.
Fig. 5(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of comparative example 1, respectively.
Fig. 6(a) and (b) are graphs of rate performance and cycle performance of aqueous zinc-ion batteries using the test electrolyte and the reference electrolyte of comparative example 2, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 2mol/L zinc sulfate and 0.3mol/L manganese sulfate, adding 200g of the mixed aqueous solution, adding 15g of ammonium alkali lignin, 15g of hydroxylation enzyme-hydrolyzed lignin, 5g of hydroxylation organic solvent lignin and 5g of amination steam explosion lignin, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 4.5 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 2mol/L zinc sulfate and 0.3mol/L manganese sulfate, and the pH value is 4.5. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 1(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly higher than that of the aqueous zinc ion battery using the reference electrolyte, which indicates that the rate performance is better; in addition, as can be seen from fig. 1(b), the initial specific capacity of the zinc ion battery at the current density of 1.5A/g is up to 250mAh/g, which is much higher than the initial specific capacity of 182mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at the current density, the specific capacity of the zinc ion battery is still much higher than that of the water-based zinc ion battery using the reference electrolyte. Therefore, the lignin-based complex electrolyte has the functions of inhibiting side reactions in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, obviously inhibiting the formation and growth of zinc dendrites and the like, and can obviously improve the rate capability and the cycle performance of the water-based zinc ion battery.
Example 2
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 2mol/L zinc trifluoromethanesulfonate and 0.5mol/L manganese trifluoromethanesulfonate, adding 200g of the mixed aqueous solution, adding 5g of hydroxylated lignosulfonate, 5g of aminated sulfonated lignin, 5g of ammonified carboxylated lignin, 15g of hydroxylated alkali lignin and 10g of ammonified enzymatic lignin, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 5.0 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 2mol/L zinc trifluoromethanesulfonate and 0.5mol/L manganese trifluoromethanesulfonate, and the pH value is 5.0. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 2(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly higher than that of the aqueous zinc ion battery using the reference electrolyte, which indicates that the rate performance is better; in addition, as can be seen from fig. 2(b), the initial specific capacity of the zinc ion battery at the current density of 1.5A/g is up to 271mAh/g, which is much higher than the initial specific capacity of 202mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at the current density, the specific capacity of the zinc ion battery is still much higher than the specific capacity of the water-based zinc ion battery using the reference electrolyte. Therefore, the lignin-based complex electrolyte has the functions of inhibiting side reactions in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, obviously inhibiting the formation and growth of zinc dendrites and the like, and can obviously improve the rate capability and the cycle performance of the water-based zinc ion battery.
Example 3
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 1mol/L zinc chloride, 0.5mol/L zinc bromide, 0.5mol/L zinc iodide, 0.3mol/L manganese chloride, 0.1mol/L manganese bromide and 0.1mol/L manganese iodide, adding 200g of ammonium lignosulfonate 5g, hydroxylated sulfonated lignin 5g, hydroxylated carboxylated lignin 5g, aminated alkali lignin 15g, aminated enzymolysis lignin 10g and ammonium organic solvent lignin 10g, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 4.3 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 1mol/L zinc chloride, 0.5mol/L zinc bromide, 0.5mol/L zinc iodide, 0.3mol/L manganese chloride, 0.1mol/L manganese bromide and 0.1mol/L manganese iodide, and the pH value is 4.3. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 3(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly higher than that of the aqueous zinc ion battery using the reference electrolyte, which indicates that the rate performance is better; in addition, as can be seen from fig. 3(b), the initial specific capacity of the zinc ion battery at the current density of 1.5A/g is up to 249mAh/g, which is much higher than the initial specific capacity of 195mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at the current density, the specific capacity of the zinc ion battery is still much higher than that of the water-based zinc ion battery using the reference electrolyte. Therefore, the lignin-based complex electrolyte has the functions of inhibiting side reactions in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, obviously inhibiting the formation and growth of zinc dendrites and the like, and can obviously improve the rate capability and the cycle performance of the water-based zinc ion battery.
Example 4
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 1mol/L zinc nitrate, 1mol/L zinc acetate, 0.5mol/L manganese nitrate and 0.5mol/L manganese acetate, adding 200g of aminated lignosulfonate, 10g of ammonium sulfonated lignin, 5g of aminated carboxylated lignin, 10g of aminated organic solvent lignin, 15g of hydroxylated steam explosion lignin and 5g of ammonium steam explosion lignin, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 4.8 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 1mol/L zinc nitrate, 1mol/L zinc acetate, 0.5mol/L manganese nitrate and 0.5mol/L manganese acetate, and the pH value is 4.8. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 4(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly higher than that of the aqueous zinc ion battery using the reference electrolyte, which indicates that the rate performance is better; in addition, as can be seen from fig. 4(b), the initial specific capacity of the zinc ion battery at the current density of 1.5A/g is as high as 217mAh/g, which is much higher than the initial specific capacity of 138mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at the current density, the specific capacity of the zinc ion battery is still higher than that of the water-based zinc ion battery using the reference electrolyte. Therefore, the lignin-based complex electrolyte has the functions of inhibiting side reactions in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, obviously inhibiting the formation and growth of zinc dendrites and the like, and can obviously improve the rate capability and the cycle performance of the water-based zinc ion battery.
Comparative example 1
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 2.5mol/L zinc sulfate and 0.5mol/L manganese sulfate, adding 200g of the mixed aqueous solution, adding 0.05g of ammonium alkali lignin and 0.05g of hydroxylase lignin-hydrolyzing, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 4.4 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 2.5mol/L zinc sulfate and 0.5mol/L manganese sulfate, and the pH value is 4.4. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 5(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly lower than that of the aqueous zinc ion battery using the reference electrolyte at the tested rate, indicating that the rate performance is worse; in addition, as can be seen from fig. 5(b), the initial specific capacity at 1.5A/g current density is about 130mAh/g, which is much lower than the initial specific capacity 185mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at this current density, the specific capacity is still lower than that of the water-based zinc ion battery using the reference electrolyte. This indicates that, when the amount of the modified lignin added is less than 0.1% by mass of the aqueous electrolyte, the lignin-based complex electrolyte does not have the functions of suppressing the side reaction in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, and suppressing the formation and growth of zinc dendrites, but a small amount of the modified lignin adversely affects the performance, resulting in a significant decrease in the rate capability and cycle performance of the aqueous zinc ion battery.
Comparative example 2
1. Test electrolyte configuration and aqueous zinc ion battery assembly based thereon:
preparing a mixed aqueous solution of 1.5mol/L zinc trifluoromethanesulfonate and 0.1mol/L manganese trifluoromethanesulfonate, adding 200g of the mixed aqueous solution, adding 80g of ammonium lignosulfonate and 80g of hydroxylated organic solvent lignin, stirring until the lignin is completely dissolved, and then adjusting the pH value of the mixed solution to 4.9 to obtain the lignin-based compound electrolyte.
And assembling the positive electrode capable of reacting with zinc ions, the diaphragm, the lignin-based compound electrolyte and the zinc negative electrode into a battery shell to obtain the water-based zinc ion battery.
2. Preparation of reference electrolyte and assembly of water-based zinc ion battery based on the reference electrolyte:
the reference electrolyte is a mixed aqueous solution of 1.5mol/L zinc trifluoromethanesulfonate and 0.1mol/L manganese trifluoromethanesulfonate, and the pH value is 4.9. The assembly process of the aqueous zinc-ion battery using the reference electrolyte was the same as above.
3. And (3) electrochemical performance testing:
the water-based zinc ion battery using the test electrolyte and the reference electrolyte is subjected to rate charge and discharge tests and constant current charge and discharge tests, wherein the set rate is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. And (4) analyzing results:
as can be seen from fig. 6(a), the specific capacity of the aqueous zinc ion battery using the test electrolyte is significantly lower than that of the aqueous zinc ion battery using the reference electrolyte at the tested rate, indicating that the rate performance is worse; in addition, as can be seen from fig. 6(b), the initial specific capacity at 1.5A/g current density is about 70mAh/g, which is much lower than the initial specific capacity 155mAh/g of the water-based zinc ion battery using the reference electrolyte, and after 1400 times of charging and discharging at this current density, the specific capacity is still lower than that of the water-based zinc ion battery using the reference electrolyte. This indicates that when the amount of the modified lignin added is much higher than 66.7% of the mass of the aqueous electrolyte, the ionic conductivity of the lignin-based complex electrolyte may be greatly reduced, so that the lignin-based complex electrolyte does not have the functions of suppressing the side reaction in the positive electrode, reducing the corrosion of the electrolyte to the zinc negative electrode, and suppressing the formation and growth of zinc dendrites, and the excessive modified lignin is adversely affected, thereby significantly reducing the rate capability and cycle performance of the aqueous zinc ion battery.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A lignin-based compound electrolyte for a water-based zinc ion battery is characterized by comprising the following components in parts by weight:
100 parts of modified lignin;
150-100000 parts of an aqueous electrolyte;
the modified lignin comprises at least one of modified products which are obtained by taking lignosulfonate, sulfonated lignin, carboxylated lignin, alkali lignin, enzymatic hydrolysis lignin, organic solvent lignin and steam explosion lignin as main raw materials and grafting hydroxyl and amino functional groups into the main raw materials through chemical modification.
2. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 1, wherein: the modified lignin comprises at least one of hydroxylated lignin sulfonate, aminated lignin sulfonate, hydroxylated sulfonated lignin, aminated sulfonated lignin, hydroxylated carboxylated lignin, aminated carboxylated lignin, hydroxylated alkali lignin, aminated alkali lignin, hydroxylated enzyme-hydrolyzed lignin, aminated enzyme-hydrolyzed lignin, hydroxylated organic solvent lignin, aminated organic solvent lignin, hydroxylated steam explosion lignin and aminated steam explosion lignin.
3. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 1, wherein: the lignin-based compound electrolyte is prepared by mixing and stirring modified lignin and water-phase electrolyte until the modified lignin is fully dissolved.
4. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 1, wherein: the pH value of the lignin-based compound electrolyte is 2-7.
5. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 1, wherein: the water-phase electrolyte is formed by mixing and dissolving water-soluble zinc salt and water-soluble manganese salt.
6. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 5, wherein: the water-soluble zinc salt comprises at least one of zinc sulfate, zinc chloride, zinc bromide, zinc iodide, zinc nitrate, zinc acetate and zinc trifluoromethanesulfonate; the water-soluble manganese salt comprises at least one of manganese sulfate, manganese chloride, manganese bromide, manganese iodide, manganese nitrate, manganese acetate and manganese trifluoromethanesulfonate.
7. The lignin-based complex electrolyte for an aqueous zinc-ion battery according to claim 5, wherein: the concentration of the water-soluble zinc salt in the water-phase electrolyte is 0.1-15 mol/L, and the concentration of the water-soluble manganese salt is 0.01-2 mol/L.
8. An aqueous zinc-ion battery comprising the lignin-based complex electrolyte according to any one of claims 1 to 7.
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| CN112467234B (en) * | 2020-12-24 | 2022-04-08 | 国家纳米科学中心 | Electrolyte for zinc secondary battery, preparation method and use thereof |
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| CN115133159A (en) * | 2022-09-01 | 2022-09-30 | 河南师范大学 | Functional aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN116005203A (en) * | 2022-12-16 | 2023-04-25 | 云南驰宏锌锗股份有限公司 | A kind of method that lignin improves the quality of cathode zinc sheet |
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