CN109671946B - Zinc ion battery positive electrode active material, positive electrode material, zinc ion battery positive electrode, zinc ion battery, and preparation method and application thereof - Google Patents
Zinc ion battery positive electrode active material, positive electrode material, zinc ion battery positive electrode, zinc ion battery, and preparation method and application thereof Download PDFInfo
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- CN109671946B CN109671946B CN201811543606.4A CN201811543606A CN109671946B CN 109671946 B CN109671946 B CN 109671946B CN 201811543606 A CN201811543606 A CN 201811543606A CN 109671946 B CN109671946 B CN 109671946B
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- ion battery
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 239000010955 niobium Substances 0.000 claims abstract description 32
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 28
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 239000002905 metal composite material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000004146 energy storage Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 239000006182 cathode active material Substances 0.000 abstract 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 98
- 238000000034 method Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 8
- 229960003351 prussian blue Drugs 0.000 description 8
- 239000013225 prussian blue Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 7
- -1 zinc aluminate Chemical class 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002843 nonmetals Chemical class 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 3
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 3
- 229910002625 H-Nb2O5 Inorganic materials 0.000 description 2
- 229910003170 M-Nb2O5 Inorganic materials 0.000 description 2
- 229910019714 Nb2O3 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical group [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明公开了一种锌离子电池正极活性材料、正极材料、锌离子电池正极、锌离子电池及其制备方法和应用，涉及锌离子电池技术领域。锌离子电池正极活性材料包括铌的氧化物或其复合材料。本发明将铌的氧化物或其复合材料用于锌离子电池的正极活性材料中，铌的氧化物或其复合材料具有快速的锌离子传输通道，可实现锌离子的快速嵌入与脱嵌，且晶体结构稳定，制备的锌离子电池具有长循环寿命、高比容量和低成本的优势，缓解了现有的锂离子电池锂资源储量有限和成本高的问题，以及目前锌离子电池正极活性材料存在的容量低、正极结构稳定性差和插层动力学缓慢等问题。
The invention discloses a positive electrode active material of a zinc ion battery, a positive electrode material, a positive electrode of the zinc ion battery, a zinc ion battery and a preparation method and application thereof, and relates to the technical field of the zinc ion battery. Positive active materials for zinc-ion batteries include niobium oxides or composites thereof. In the present invention, the oxide of niobium or the composite material thereof is used in the positive electrode active material of the zinc ion battery, and the oxide of niobium or the composite material thereof has a fast zinc ion transmission channel, which can realize the fast intercalation and deintercalation of zinc ions, and The crystal structure is stable, and the prepared zinc-ion battery has the advantages of long cycle life, high specific capacity and low cost, which alleviates the problems of limited lithium resource reserves and high cost of existing lithium-ion batteries, as well as the existence of current zinc-ion battery cathode active materials. The low capacity, poor structural stability of the cathode, and sluggish intercalation kinetics are also encountered.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a zinc ion battery positive electrode active material, a positive electrode material, a zinc ion battery positive electrode, a zinc ion battery and a preparation method and application thereof.
Background
With the popularization of portable electronic devices such as computers, mobile phones and tablets and the rapid development of green and environment-friendly electric automobiles, people have an increasing demand for secondary batteries, and lithium ion batteries also have some defects as secondary batteries with the most extensive applications: the price of lithium resources rises year by year due to shortage of the lithium resources, lithium dendrite is easy to form on a negative electrode to cause short circuit, organic electrolyte is flammable, and certain potential safety hazards exist. Therefore, it is necessary to find a new type of secondary battery to replace the lithium ion battery.
Compared with lithium, zinc has more abundant resources and lower cost, and the water system zinc ion battery eliminates the danger of fire, explosion and the like possibly caused by organic electrolyte. In addition, 2 electrons are transferred in the oxidation-reduction process of zinc ions, so that the zinc ions have better performanceHigh theoretical capacity (820 mAh/g). However, due to the large ionic radius of zinc, Zn can be reversibly inserted and extracted2+Is not much. The anode active materials of the water-based zinc ion battery reported at present mainly comprise manganese oxide, vanadium oxide, Prussian blue and other materials. However, manganese oxide is easily dissolved in the circulation process, so that the capacity is greatly reduced, the raw materials of vanadium oxide, prussian blue and derivatives thereof have high toxicity, and the capacities of prussian blue and derivatives thereof are generally low.
Accordingly, it is desirable to provide a better capacity zinc ion battery positive electrode active material that can solve at least one of the above problems.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a zinc ion battery anode active material, which solves the problems of low capacity, poor anode structure stability, slow intercalation kinetics and the like of the conventional zinc ion battery.
The other purpose of the invention is to provide a zinc ion battery positive electrode, which comprises the zinc ion battery positive electrode material and has the same advantages as the positive electrode material.
The invention also aims to provide a zinc ion battery positive electrode, which comprises the zinc ion battery positive electrode material and has the same advantages as the positive electrode material.
The fourth purpose of the invention is to provide a preparation method of the zinc ion battery anode, which is simple.
The fifth object of the present invention is to provide a zinc ion battery, which comprises the above-mentioned positive electrode, and has high specific capacity and long cycle life.
The invention also aims to provide a preparation method of the zinc ion battery, which is simple and feasible.
The seventh purpose of the present invention is to provide an application of the above zinc ion battery in electric tools, electronic devices, electric vehicles or large-scale energy storage devices.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a positive active material for a zinc-ion battery, comprising an oxide of niobium or a composite thereof.
Preferably, on the basis of the technical scheme of the invention, the oxide of niobium comprises NbO and Nb2O3、 NbO2Or Nb2O5Preferably Nb2O5；
Preferably, Nb2O5The crystalline form of (a) includes an orthorhombic phase, a hexagonal phase or a monoclinic phase, preferably a hexagonal phase.
Preferably, based on the technical scheme of the invention, the oxide composite material of niobium comprises an oxide/metal composite material or an oxide/nonmetal composite material of niobium, and the oxide/metal composite material of niobium is preferably Nb2O5/metal composite material or Nb2O5A non-metallic composite material;
preferably, Nb2O5The composition general formula of the/metal composite material is MxNb2O5Wherein x is more than 0 and less than 1; m comprises one or more of Zn, Li, Na, K, Ti, V, Al or Ca, preferably Li, Ti or V, and further preferably Li;
preferably, Nb2O5The nonmetal in the nonmetal composite material is a carbon material, a nitrogen material, a sulfur material, a phosphorus material or a silicon material;
preferably, the carbon material comprises one or more of graphene, carbon nanotubes, soft carbon, hard carbon or carbon fibers; preferably, Nb2O5The carbon content in the carbon/carbon composite material is 0.5-20 wt%.
Preferably, Nb2O5The composite material comprises Nb2O5/Si、Nb2O5/C、Nb2O5/S、Nb2O5/N、 Nb2O5/P、LixNb2O5、KxNb2O5、NaxNb2O5、CaxNb2O5、ZnxNb2O5、TixNb2O5Or VxNb2O5Preferably LixNb2O5。
In a second aspect, the invention provides a zinc ion battery positive electrode material, which comprises the zinc ion battery positive electrode active material.
In a third aspect, the invention provides a zinc ion battery positive electrode, which comprises a positive electrode current collector and the zinc ion battery positive electrode material.
In a fourth aspect, the invention provides a preparation method of the positive electrode of the zinc ion battery, which comprises the following steps:
and mixing the zinc ion battery positive electrode material, a conductive agent, a binder and a solvent to prepare slurry, and coating the slurry on the surface of a positive electrode current collector to obtain the zinc ion battery positive electrode.
In a fifth aspect, the invention provides a zinc ion battery, which comprises the positive electrode of the zinc ion battery or the positive electrode of the zinc ion battery prepared by the preparation method, a negative electrode, a diaphragm and an electrolyte.
Preferably, on the basis of the technical scheme of the invention, the negative electrode is metal zinc, preferably zinc foil;
preferably, the electrolyte is an aqueous solution containing a zinc salt.
Preferably, the zinc salt comprises one or more of zinc chloride, zinc aluminate, zinc sulfate, zinc perchlorate, zinc nitrate, zinc trifluoromethanesulfonate, zinc oxalate or zinc acetate;
preferably, the concentration of the zinc salt in the electrolyte is 0.1-10 mol/L.
In a sixth aspect, the invention provides a preparation method of the zinc ion battery, which comprises the following steps:
and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte of the zinc ion battery to obtain the zinc ion battery.
In a seventh aspect, the invention provides an application of the above zinc ion battery in electric tools, electronic equipment, electric vehicles or large-scale energy storage equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) the positive active material of the zinc ion battery comprises niobium oxide or a composite material thereof, the niobium oxide or the composite material thereof is used in the positive active material of the zinc ion battery, the niobium oxide or the composite material thereof has a rapid zinc ion transmission channel, the rapid embedding and de-embedding of zinc ions can be realized, the crystal structure is stable, the prepared zinc ion battery has the advantages of long cycle life, high specific capacity and low cost, the problems of limited lithium resource reserve and high cost of the existing lithium ion battery are solved, the problems of low capacity, poor positive structure stability, slow intercalation dynamics and the like of the existing positive active material of the zinc ion battery are solved, and the positive active material of the zinc ion battery can be applied to the fields of electric tools, electronic equipment, electric vehicles or large-scale energy storage and the like.
(2) As a preferred embodiment, an aqueous zinc ion battery using an oxide of niobium or a composite material thereof as a positive electrode active material and a zinc sheet as a positive electrode has the above advantages and also has an advantage of high safety.
Drawings
Fig. 1 is a schematic structural view of a zinc-ion battery according to an embodiment of the present invention.
The figure is as follows: 1-a negative electrode; 2-an electrolyte; 3-a separator; 4-a positive electrode active material layer; 5-positive electrode current collector.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided a positive active material for a zinc-ion battery comprising an oxide of niobium or a composite material thereof.
The zinc ion battery is a secondary battery using zinc ions as a transmission medium.
Currently, the positive active material of the zinc ion battery mainly comprises manganese oxide, vanadium oxide or Prussian blue. These materials all suffer from low capacity, slow ion kinetics, etc.
The invention uses the niobium oxide or the composite material thereof in the positive active material of the zinc ion battery.
"oxide of niobium or a composite thereof" means an oxide of niobium or an oxide composite of niobium.
The niobium oxides, wherein niobium is present predominantly in the +5, +4, +3, and +2 valences, include, but are not limited to, NbO, Nb2O3、NbO2Or Nb2O5. The oxide of niobium belongs to the n-type transition metal oxide.
In a preferred embodiment, the oxide of niobium is Nb2O5。
The crystal form of the oxide of niobium is not limited, for example, Nb2O5The crystal form of (A) comprises H-Nb2O5(corresponding to pseudo-hexagonal phase), O-Nb2O5(corresponding to orthogonal phase), T-Nb2O5(corresponding to orthorhombic phase), TT-Nb2O5(corresponding to hexagonal phase) or M-Nb2O5(corresponding to monoclinic phase) and the like.
The morphology of the oxide of niobium is not limited, and may be a one-dimensional nanostructure such as a nanofiber or a nanobelt, or a two-dimensional structure such as a nanosheet.
The source of the niobium oxide is not limited, and the niobium oxide can be directly obtained by commercial products or self-preparation, and can be prepared by the existing preparation method of the nano material, including a solid phase method, a liquid phase method or a gas phase method, wherein the solid phase method mainly comprises a high-temperature self-propagating synthesis method and a salt direct thermal decomposition method, the liquid phase method mainly comprises a sol-gel method, a hydrothermal method, a microemulsion method or a coprecipitation method, and the gas phase method mainly comprises a gas phase deposition method, a gas phase decomposition method or a gas phase reaction method.
The "oxide composite material of niobium" is a composite material of an oxide of niobium combined with other metals and/or nonmetals, where the metals are other metals than niobium, including but not limited to Zn, Li, Na, K, Ti, V, Al, Ca, etc., and the nonmetals include but not limited to C, N, O, P, S, Si, etc., and the form of the oxide composite material of niobium is not limited, and may be an oxide-doped material of niobium or an oxide-coated material of niobium.
In a preferred embodiment, the niobium oxide composite material is Nb2O5A composite material.
Nb2O5The composite material may be Nb2O5A/metal composite material, which may also be Nb2O5Non-metallic composite material. "Nb2O5In the case of the metal composite material, "/" means "and".
Preferably, Nb2O5The composition general formula of the/metal composite material is MxNb2O5Wherein x is more than 0 and less than 1; m comprises one or more of Zn, Li, Na, K, Ti, V, Al or Ca.
Nb2O5The composite material may be represented as Nb2O5A can be metal, such as one or more of Zn, Li, Na, K, Ti, V, Al or Ca, or non-metal, such as one or more of C, N, O, P, S or Si.
The crystal form and the morphology of the oxide composite material of niobium are not limited.
The positive active material of the zinc ion battery comprises niobium oxide or a composite material thereof, the niobium oxide or the composite material thereof is used in the positive active material of the zinc ion battery, the niobium oxide has a rapid zinc ion transmission channel, the rapid embedding and de-embedding of zinc ions can be realized, the crystal structure is stable, the prepared zinc ion battery has the advantages of long cycle life, high specific capacity and low cost, the problems of limited lithium resource storage capacity and high cost of the existing lithium ion battery are solved, and the problems of low capacity, poor positive structure stability, slow intercalation dynamics and the like of the positive active material of the existing zinc ion battery can be applied to the fields of large-scale energy storage and the like.
In one embodiment, Nb2O5The crystal form of (A) is a hexagonal phase.
Nb in hexagonal crystal form2O5The prepared zinc ion battery has higher specific capacity and cycle life.
In one embodiment, Nb2O5The composition formula of the/metal composite material is MxNb2O5Wherein M is Li, Ti or V, and more preferably Li.
Nb by doping with Li, Ti or V metals2O5The material is more beneficial to accelerating the transmission of zinc ions, and the zinc ion battery with more excellent specific capacity and cycle life is obtained.
In one embodiment, Nb2O5The composite material is Nb2O5A carbon composite material.
The type of carbon is not limited, and typically but not by way of limitation, includes one or more of graphene, carbon nanotubes, soft carbon, hard carbon, or carbon fibers, for example.
Preferably, Nb2O5The carbon content of the/carbon composite is 0.5 to 20 wt.%, for example 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15% or 20%.
Carbon-compounded Nb2O5Further promote Nb2O5The conductivity of the zinc-ion battery is beneficial to obtaining the zinc-ion battery with more excellent specific capacity and cycle life.
In one embodiment, Nb2O5The composite material may also be MxNb2O5and/C (metal and carbon are compounded together, and the "/" represents the meaning of "and"), wherein M can be one or more of Zn, Li, Na, K, Ti, V, Al or Ca, and C can be one or more of graphene, carbon nano-tube, soft carbon, hard carbon or carbon fiber.
By pairing Nb2O5The obtained zinc ion battery can further improve the capacity and the cycle life by compounding the metal and the carbon.
In one embodiment, Nb2O5The composite material comprises Nb2O5/Si、Nb2O5/C、Nb2O5/S、 Nb2O5/N、Nb2O5/P、LixNb2O5、KxNb2O5、NaxNb2O5、CaxNb2O5、ZnxNb2O5、 TixNb2O5Or VxNb2O5Preferably LixNb2O5。
By selecting Nb2O5The composite material can obtain the zinc ion battery with better electrical property.
In one embodiment, the zinc-ion battery positive active material further comprises a conductive agent and a binder.
It is to be understood that the kind of the conductive agent and the binder is not particularly limited, and a conductive agent and a binder, which are conventional in the art, may be used. The conductive agent includes, but is not limited to, one or more of conductive carbon spheres, conductive graphite, conductive carbon black, conductive carbon fibers, graphene, reduced graphene oxide, or carbon nanotubes. The binder includes but is not limited to one or more of polyvinyl alcohol, polyvinylidene fluoride, polytetrafluoroethylene, carboxymethyl cellulose, polyolefins or SBR rubber.
The proportions of the niobium oxide or its composite material, the conductive agent and the binder are not limited, and the conventional proportions of the positive electrode active material, the conductive agent and the binder in the technical field of zinc ion batteries can be adopted.
According to a second aspect of the present invention, there is provided a zinc ion battery positive electrode material comprising the above zinc ion battery positive electrode active material.
The positive electrode material of the zinc ion battery has the same advantages as the positive electrode active material of the zinc ion battery, and the description is omitted.
According to a third aspect of the present invention, there is provided a zinc ion battery positive electrode comprising a positive electrode current collector and the above zinc ion battery positive electrode material.
The positive current collector is not limited, and includes, but is not limited to, any one of aluminum foil, carbon-coated aluminum foil, nickel mesh, foamed nickel, titanium foil, an alloy containing at least one of them, or a composite material containing at least one of them, preferably titanium foil.
The positive electrode of the zinc ion battery has the same advantages as the positive electrode material of the zinc ion battery.
According to a fourth aspect of the present invention, there is provided a method for preparing the positive electrode of the zinc ion battery, comprising the following steps:
and mixing the zinc ion battery positive electrode material, a conductive agent, a binder and a solvent to prepare slurry, and coating the slurry on the surface of a positive electrode current collector to obtain the zinc ion battery positive electrode.
Solvents include, but are not limited to, NMP (N-methylpyrrolidone) or water.
The anode material is made into slurry and coated to form an anode material layer, so that the anode is obtained, and the preparation is simple.
According to a fifth aspect of the invention, a zinc ion battery is provided, which comprises the positive electrode of the zinc ion battery or the positive electrode of the zinc ion battery prepared by the preparation method, a negative electrode, a diaphragm and an electrolyte.
The zinc ion battery comprises the zinc ion battery anode, and the zinc ion battery prepared by adopting the niobium oxide and the composite material thereof as the anode active material has the advantages of high specific capacity, long cycle life and low cost.
In one embodiment, the negative electrode is metallic zinc, preferably zinc foil.
The zinc ion battery cathode adopts a zinc sheet, and a zinc ion battery system formed by the zinc sheet and the niobium oxide or the composite material anode material thereof has high specific capacity and cycle life performance.
The electrolyte may be an aqueous electrolyte or a nonaqueous electrolyte.
Preferably, the electrolyte is an aqueous electrolyte.
The aqueous electrolyte is adopted to avoid the danger of fire, explosion and the like possibly caused by adopting the organic electrolyte, and the safety is higher.
An exemplary zinc ion battery structure is shown in fig. 1, and comprises a negative electrode 1, a positive electrode of the zinc ion battery or a positive electrode prepared by the preparation method of the positive electrode of the zinc ion battery, an electrolyte 2 between the positive electrode and the negative electrode, and a diaphragm 3; the positive electrode current collector 5 is provided with a positive electrode active material layer 4.
Preferably, the negative electrode is a zinc foil.
Preferably, the electrolyte is an aqueous solution containing a zinc salt.
Preferably, the zinc salt comprises one or more of zinc chloride, zinc aluminate, zinc sulfate, zinc perchlorate, zinc nitrate, zinc trifluoromethanesulfonate, zinc oxalate or zinc acetate.
Preferably, the concentration of the zinc salt in the electrolyte is 0.1 to 10mol/L, including but not limited to 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 2mol/L, 6mol/L or 10 mol/L.
The separator is not particularly limited, and may be one of common separators currently used in the art, including, but not limited to, a porous ceramic film, a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, or a glass fiber paper.
The structural shape of the zinc ion battery is not limited, and the zinc ion battery can be a button battery, a columnar battery or a soft package battery.
According to a sixth aspect of the present invention, there is provided a method for manufacturing the above zinc ion battery, comprising the steps of:
and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte of the zinc ion battery to obtain the zinc ion battery.
It is to be understood that the manner of assembling the cathode, the anode, the separator, and the electrolyte is not particularly limited. The preparation method is simple and feasible.
In one embodiment, a method of making a zinc-ion battery includes the steps of:
preparing a positive electrode: weighing the positive active material, the conductive agent and the binder according to a certain proportion, adding a solvent, and uniformly mixing to obtain slurry; uniformly coating the slurry on the surface of a titanium foil, drying, pressing and cutting into required sizes to obtain a positive electrode;
preparing a negative electrode: cutting the zinc foil into required size, and cleaning and drying the surface to obtain the cathode;
and assembling the battery in a conventional room temperature environment, tightly stacking the prepared cathode, the diaphragm and the battery anode in sequence, adding electrolyte to completely soak the diaphragm, and then packaging the stacked part into a battery shell to finish the battery assembly.
According to a seventh aspect of the present invention, there is provided a use of a zinc ion battery in a power tool, an electronic device, an electric vehicle or a large-sized energy storage device.
Power tools use zinc ion batteries as a driving power source to move parts, including but not limited to electric drills and the like; the electronic device is a zinc ion battery as an operating power supply to perform various functions, including but not limited to a mobile phone, a notebook computer, a desktop computer or an electronic watch; the electric vehicle is an electric vehicle which runs by using a zinc ion battery as a driving power supply, and comprises but is not limited to an electric vehicle and the like; the large-scale energy storage equipment uses zinc ion batteries as energy storage units, and includes but is not limited to substations or wind generating sets and the like.
The same effect can be obtained by using the zinc ion battery of the invention for electric tools, electronic equipment, electric vehicles or large-scale energy storage equipment.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for purposes of illustration only and are not to be construed as limiting the invention in any way.
Example 1
A zinc ion battery, the positive active material adopts T-Nb2O5And the negative electrode is a zinc sheet.
The preparation method of the zinc ion battery comprises the following steps:
(1) preparing a niobium pentoxide positive electrode: adding 0.7g of niobium pentoxide powder, 0.2g of carbon black and 0.1g of polyvinylidene fluoride into an agate mortar, fully grinding, and then dripping a proper amount of N-methyl pyrrolidone to mix into uniform slurry; then uniformly coating the slurry on the surface of a titanium foil (positive electrode current collector), drying in vacuum, cutting the dried electrode slice into wafers with the diameter of 12mm, and compacting to obtain a positive electrode;
(2) preparing a zinc sheet cathode: cutting the zinc foil into a wafer with the diameter of 14mm, and cleaning and drying to obtain a negative electrode;
(3) preparing electrolyte: dissolving 3.27g of zinc trifluoromethanesulfonate in 3mL of deionized water (3M), and stirring to fully dissolve the zinc trifluoromethanesulfonate to obtain an electrolyte;
(4) preparing a diaphragm: cutting the glass fiber into a wafer with the diameter of 16mm, and drying for later use;
(5) and assembling the battery at room temperature, tightly stacking the prepared cathode, the diaphragm and the battery anode in sequence, adding electrolyte to completely soak the diaphragm, and packaging the stacked part into a battery shell to finish the battery assembly.
Examples 2 to 4
Examples 2 to 4 differ from example 1 only in that the crystal forms of the positive electrode active materials are different, as specifically shown in table 1.
TABLE 1
| Example numbering | Positive electrode active material |
| 1 | T-Nb2O5 |
| 2 | H-Nb2O5 |
| 3 | O-Nb2O5 |
| 4 | M-Nb2O5 |
Examples 5 to 13
Examples 5 to 13 differ from example 1 only in that the materials compounded in the positive electrode active material were different (the content of the composite material was 10 wt% of the positive electrode active material, and x was 0.2), as specifically shown in table 2.
TABLE 2
Examples 14 to 17
Examples 14 to 17 differ from example 1 only in the carbon content of the positive electrode active material, as shown in table 3.
TABLE 3
| Example numbering | Positive electrode active material | Carbon content (wt%) |
| 1 | Nb2O5 | 0 |
| 14 | Nb2O5/C | 0.5 |
| 15 | Nb2O5/ |
5 |
| 16 | Nb2O5/C | 15 |
| 17 | Nb2O5/C | 20 |
Examples 18 to 21
Examples 18 to 21 differ from example 1 only in the amount of doping in the positive electrode active material, as shown in table 4.
TABLE 4
Examples 22 to 27
Examples 22 to 27 differ from example 1 only in the electrolyte salt, as shown in table 5.
TABLE 5
| Example numbering | |
| 1 | Zinc trifluoromethanesulfonate (CTF) |
| 22 | Zinc chloride |
| 23 | Zinc sulfate |
| 24 | Zinc nitrate |
| 25 | Zinc perchlorate |
| 26 | Zinc acetate |
| 27 | Zinc oxalate |
Examples 28 to 31
Examples 28-31 differ from example 1 only in the separator used, as shown in table 6.
TABLE 6
Comparative example 1
The positive active material of zinc ion battery adopts alpha-MnO2And the negative electrode is a zinc sheet.
A zinc ion battery was fabricated by a method different from that of example 1 in that niobium pentoxide was replaced with α -MnO2。
Comparative example 2
A zinc ion battery adopts V as positive electrode active material2O5And the negative electrode is a zinc sheet.
A zinc ion battery was fabricated in a manner different from that of example 1 in that niobium pentoxide was replaced with V2O5。
Comparative example 3
A zinc ion battery adopts Prussian blue FeHCF as a positive active material and zinc sheets as a negative electrode.
The zinc ion battery was prepared by a method different from that of example 1 in that niobium pentoxide was replaced with prussian blue FeHCF.
Comparative example 4
A magnesium ion battery and a method for preparing the same, which are different from example 1 in that an electrolyte salt of zinc trifluoromethanesulfonate is replaced with magnesium trifluoromethanesulfonate.
Test examples
The electrochemical performance tests of the zinc ion batteries obtained in the examples 1 to 31 and the comparative examples 1 to 4 are carried out, the battery tests comprise specific capacity and cycle number, and the specific test method comprises the following steps:
specific capacity: the cyclic charge and discharge is carried out on a CT2001A battery cyclic test system, the standard capacity of an electrode is tested by charging and discharging with a current density of 50mA/g, the voltage interval is 0.6-1.8V, the specific capacity of a material is the integral of the current multiplied by the time divided by the mass of a positive electrode active material (C ═ It/m), and the charge and discharge process is as follows: standing for 600s, and then performing charge-discharge circulation, wherein the circulation step comprises the following steps: constant current discharge-constant current charge.
Cycle number: the cycle performance of the battery is tested by charging and discharging at a current density of 50mA/g on a battery cycle test system, the cycle performance of the battery is represented by the number of cycles when the discharge depth (DOD) of the battery is reduced to 80%, the battery is kept still for 600s and then subjected to charge and discharge cycles, and the cycle steps are the same as the cycle charge and discharge.
The results are shown in Table 7.
TABLE 7
As can be seen from table 7, the zinc ion battery having the positive electrode made of niobium oxide or a composite material thereof has a high specific capacity and a long cycle life. Therefore, the niobium oxide or the composite material thereof has a stable crystal structure, has a rapid zinc ion transmission channel, and can realize rapid intercalation and deintercalation of zinc ions. The zinc ion battery made of positive active materials such as manganese oxide, vanadium oxide or Prussian blue has lower specific capacity, and the vanadium oxide or Prussian blue has certain toxicity.
Comparative example 4 using an oxide of niobium or a composite material thereof in a magnesium ion battery system, it can be seen that the performance of the magnesium ion battery is not very good, being inferior to that of the zinc ion battery.
Comparison of examples 2-4 with example 1 shows that Nb is2O5The crystal form influences the performance of the zinc ion battery, wherein T-Nb2O5The zinc ion battery prepared by the crystal form has better performance. The zinc ion battery performance of the examples 5-13 is further improved after other metals or nonmetals are compounded. Examples 14-17 use Nb with varying carbon content2O5Examples 18 to 21 using Li with different Li doping amountsxNb2O5The performance of zinc ion batteries varies. The comparison of examples 22-27 with example 1 shows that the use of zinc hexafluorophosphate triflate is more effective. Comparison of examples 28-31 with example 1 shows that the separator has an effect on the battery performance, and the effect is better with the glass fiber separator.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (11)
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