CN116598703A - Black phosphorus modified composite diaphragm for water-based zinc ion battery and preparation method and application thereof - Google Patents
Black phosphorus modified composite diaphragm for water-based zinc ion battery and preparation method and application thereof Download PDFInfo
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- CN116598703A CN116598703A CN202310497121.0A CN202310497121A CN116598703A CN 116598703 A CN116598703 A CN 116598703A CN 202310497121 A CN202310497121 A CN 202310497121A CN 116598703 A CN116598703 A CN 116598703A
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- black phosphorus
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 108
- 239000012528 membrane Substances 0.000 claims description 41
- 210000004027 cell Anatomy 0.000 claims description 31
- 239000003365 glass fiber Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 210000000170 cell membrane Anatomy 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 50
- 229910052725 zinc Inorganic materials 0.000 abstract description 45
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 abstract description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002033 PVDF binder Substances 0.000 description 14
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006011 Zinc phosphide Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 229940048462 zinc phosphide Drugs 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
Abstract
The invention relates to the technical field of zinc ion batteries, and discloses a black phosphorus modified composite diaphragm for a water-based zinc ion battery, and a preparation method and application thereof, wherein the preparation method comprises the following steps: and (3) placing the black phosphorus in the solution, carrying out ultrasonic stripping to obtain black phosphorus dispersion liquid, placing the battery diaphragm in the black phosphorus dispersion liquid, carrying out ultrasonic treatment on the battery diaphragm, taking out the battery diaphragm, and drying to obtain the black phosphorus modified composite diaphragm. The black phosphorus in the modified composite diaphragm can gradually react with water in the water-based electrolyte to hydrolyze and generate a zinc phosphate interface layer with the zinc surface, thereby inhibiting the growth of zinc dendrites, inhibiting the hydrogen evolution activity and prolonging the cycle life of the zinc cathode. The method can be applied to a water-based zinc ion battery, prolongs the short-circuit time, and prolongs the cycle life and capacity of the battery.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a black phosphorus modified composite diaphragm for a water-based zinc ion battery, and a preparation method and application thereof.
Background
The lithium ion battery based on the liquid organic electrolyte widely used at present has a great potential safety hazard due to the high flammability of the organic liquid, which is verified in a plurality of combustion/explosion accidents of the lithium ion battery energy storage power station at home and abroad. Therefore, there is an urgent need to develop more safe and reliable electrochemical energy storage systems.
Metal batteries based on aqueous electrolytes present great advantages in this respect due to the intrinsically safe nature of aqueous electrolytes. Conventional alkaline metal batteries (e.g., li, na, and K) react vigorously with water, resulting in serious side reactions. Therefore, researchers have paid more attention to aqueous multivalent metal (e.g., ca, mg, al, mn, zn and Fe) batteries in recent years. Among these, zn metal has moderate para-hydrogen potential, so that it can balance the side reaction of hydrogen evolution and the voltage output platform of full cell. In addition, zn metal has a theoretical mass specific capacity (820 mAh g -1 ) Specific volume capacity (5855 mAh cm) -3 ) The advantages of higher deposition/dissolution dynamics, abundant reserves, low cost, environmental friendliness and the like are outstanding among a plurality of metal anodes, and the metal anodes are paid attention in recent years.
However, at present, zinc metal batteries have not been commercialized on a large scale, mainly because zinc cathode sides are widely subjected to scientific problems such as corrosion, hydrogen evolution, dendrite growth, interface passivation and the like, so that the cathode cycling stability is limited. CN 114725537a discloses a water-based zinc ion battery electrolyte capable of inhibiting zinc dendrite and side reaction and application thereof, wherein the electrolyte comprises zinc sulfate, deionized water, and organic additives of tripropylene glycol and propylene glycol from the viewpoint of modification of the electrolyte. By changing the volumes of tripropylene glycol and propylene glycol additives, mixed electrolyte with different volume ratios is obtained. The electrolyte containing tripropylene glycol and propylene glycol additives can effectively improve the reversibility of the metal zinc cathode, reduce the occurrence of side reactions of the battery, and obtain the water-based zinc-ion battery with long service life, excellent performance and high safety.
CN114824236a discloses a water-based zinc ion battery cathode material with a functional protective layer and a preparation method thereof, wherein a zinc sheet is used as a substrate, zinc sulfate heptahydrate, sodium phosphite, stannous chloride dihydrate, boric acid, sodium sulfate, disodium ethylenediamine tetraacetate and deionized water are mixed to form an electroplating solution, and tin-doped zinc phosphide is uniformly deposited on the zinc sheet by an electrodeposition method to form a coating (zn@sn-ZnP). The invention constructs Sn-ZnP functional protective layer on the surface of the metallic zinc anode, inserts P into Zn crystal lattice to form ZnP protective layer by an economic and efficient electrodeposition method, and is beneficial to Zn 2+ And reduces the electrochemical reaction energy barrier during Zn plating/stripping; meanwhile, znSn alloy formed by electrodeposition can effectively inhibit hydrogen evolution reaction of a zinc electrode and generation of irreversible byproducts, so that the cycle life of the battery is prolonged. However, the method has the problems of insufficient and durable protection effect, limited battery performance improvement effect or complex preparation method of the zinc sheet electrode.
The current widely used diaphragm (such as glass fiber) of the zinc ion battery can only provide the function of isolating the anode and the cathode, and is difficult to generate the inhibition effect on the scientific problems of the cathode. It is therefore of great importance to further develop membrane materials which can ameliorate the above-mentioned scientific problems, especially with a continuous effect.
Disclosure of Invention
Aiming at the problems that a zinc negative electrode of a water-based zinc ion battery is easy to corrode, dendrite growth exists and interface passivation exists, the invention provides the composite diaphragm capable of continuously improving the stripping/deposition stability of the zinc negative electrode and the preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a black phosphorus modified composite membrane for a water-based zinc ion battery comprises the following steps: and (3) placing the black phosphorus in the solution, carrying out ultrasonic stripping to obtain black phosphorus dispersion liquid, placing the battery diaphragm in the black phosphorus dispersion liquid, carrying out ultrasonic treatment on the battery diaphragm, taking out the battery diaphragm, and drying to obtain the black phosphorus modified composite diaphragm.
In some embodiments, the black phosphorus ultrasonic stripping time is greater than 30 minutes. The black phosphorus block is effectively stripped by ultrasonic stripping to form a uniformly dispersed black phosphorus dispersion liquid.
In some embodiments, the battery separator is sonicated in the black phosphorus dispersion for a period of time of 15 to 30 minutes. The diaphragm base structure is easy to break after a long time. Such as 20 minutes, 25 minutes, or any value therebetween.
In some embodiments, the solution comprises a mixed solution of one or more of water, ethanol, NMP, IPA, DMF, DMSO; the black phosphorus solid can be effectively dispersed by adopting common polar solvents.
In some embodiments, the battery separator includes a composite membrane of any one or more of a fiberglass membrane, a polyolefin membrane, a cellulose membrane, a Nafion membrane. A glass fiber film is preferable, which has excellent electrolyte wettability.
In some embodiments, the black phosphorus dispersion has a black phosphorus mass concentration of 5-20mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The loading amount of black phosphorus in the black phosphorus modified composite membrane is 0.6-2.5mg cm -2 The zinc phosphate protective layer formed by hydrolysis under the condition has moderate thickness, and the battery performance is excellent after the zinc phosphate protective layer is applied to a battery, and the short-circuit time of a short-circuit battery can exceed more than 1500 hours.
In some embodiments, the black phosphorus dispersion has a black phosphorus mass concentration of 5-15mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The loading amount of the black phosphorus in the black phosphorus modified composite membrane is 1.5-2.5mg cm -2 。
In some embodiments, the drying conditions are 50-80 ℃ for 6-18 hours.
The invention also provides the black phosphorus modified composite membrane prepared by the preparation method and application of the black phosphorus modified composite membrane in a water-based zinc ion battery. Including application to zinc-zinc symmetrical cells or zinc-hydrated vanadium pentoxide full cells. The method is applied to the zinc-zinc symmetrical battery, and the short-circuit time of the battery is obviously prolonged.
The invention also provides a zinc-hydrated vanadium pentoxide full battery, wherein the black phosphorus modified composite diaphragm is used as a battery diaphragm, zinc salt aqueous solution is used as electrolyte, zinc foil is used as a negative electrode and a counter electrode, hydrated vanadium pentoxide is used as a positive electrode, and the cycle life and capacity of the full battery are obviously improved.
In some embodiments, the zinc salt comprises ZnSO 4 ,Zn(TFSI) 2 ,Zn(TfO) 2 And the like. In some embodiments, the molar concentration of zinc salt in the aqueous electrolyte is 2 to 3mol L -1 . Too low a concentration can result in too much unsolvated water in the electrolyte, resulting in too fast hydrolysis; too low a concentration may result in too little unsolvated water in the electrolyte and slow hydrolysis.
In some embodiments, the hydrated vanadium pentoxide positive electrode preparation flow comprises: will V 2 O 5 Powder sum H 2 O 2 Added to deionized water. After aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried.
The hydrated vanadium pentoxide powder was mixed with polyvinylidene fluoride (PVDF). The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying in a vacuum oven to obtain the hydrated vanadium pentoxide anode.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the battery diaphragm is modified by black phosphorus, and the black phosphorus in the modified composite diaphragm gradually reacts with water in the water-based electrolyte to hydrolyze and generate a zinc phosphate interface layer with the zinc surface, so that the growth of zinc dendrites is inhibited, the hydrogen evolution activity is inhibited, and the cycle life of a zinc cathode is prolonged. Compared with strategies such as (i) unmodified diaphragm, (ii) unmodified diaphragm+zinc anode surface zinc phosphate pre-construction, (iii) unmodified diaphragm+electrolyte phosphoric acid pre-addition, the black phosphorus modified diaphragm can realize better zinc metal stripping/deposition stability, the short-circuit time of the zinc-zinc symmetrical battery is prolonged, and the cycle life and capacity of the zinc-hydrated vanadium pentoxide full battery are greatly improved.
Drawings
FIG. 1 is a diagram showing a black phosphorus-modified glass fiber separator #1 according to example 1.
FIG. 2 is a scanning electron microscope image and an element distribution diagram of a black phosphorus-modified glass fiber septum #1 of example 1.
FIG. 3 is a graph of voltage versus time for a zinc-zinc symmetric cell assembled with black phosphorus modified fiberglass separator #1 of example 1
Fig. 4 is a graph of the cycling performance of the zinc-hydrated vanadium pentoxide full cell assembled by the black phosphorus modified glass fiber separator #1 of example 1.
FIG. 5 is a drawing showing a glass fiber separator of comparative example 1.
FIG. 6 is a scanning electron microscope image of a glass fiber membrane of comparative example 1.
Fig. 7 is a graph of voltage versus time for a zinc-zinc symmetric cell assembled from comparative example 1 fiberglass separator.
FIG. 8 is a graph showing the distribution of zinc phosphate on the surface of a zinc anode after immersing the zinc anode in phosphoric acid in comparative example 2, wherein a is the surface PO of the zinc sheet 4 And b is a corresponding side view.
Fig. 9 is a graph of voltage versus time for a zinc-zinc symmetric cell assembled from comparative example 2 fiberglass separator.
Fig. 10 is a graph of voltage versus time for a zinc-zinc symmetric cell assembled from comparative example 3 fiberglass separator.
Fig. 11 is a scanning electron microscope image of the surface of a zinc anode for 100 hours of cycling of the symmetrical battery in example 1.
Fig. 12 is a scanning electron microscope image of the surface of the zinc anode of the symmetric cell cycle of comparative example 1 for 100 hours.
FIG. 13 is a surface scanning electron microscope image of the morphology of the zinc negative electrode after 300 hours of cycling of the symmetric cell of example 1, comparative examples 2-3, (a) example 1, (b) comparative example 2, and (c) comparative example 3.
Fig. 14 is a cross-sectional scanning electron microscope image of the morphology of the zinc anode after 300 hours of cycling of the symmetric cell of example 1, comparative examples 2-3, (a) example 1, (b) comparative example 2, and (c) comparative example 3.
FIG. 15 is an ionic conductivity test chart during the hydrolysis of black phosphorus in 2M zinc sulfate electrolyte in example 4.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
The method for calculating the black phosphorus load on the diaphragm comprises the following steps: weighing an untreated battery diaphragm with the diameter of 14mm to obtain m 0 Ultrasonic treating the battery diaphragm in black phosphorus dispersion, taking out, drying, weighing and marking as m 1 The loading capacity of black phosphorus on the modified composite diaphragm is m 1 -m 0 Area.
Example 1
Preparation of black phosphorus modified glass fiber diaphragm #1 and application of black phosphorus modified glass fiber diaphragm #1 in water-based zinc battery
The black phosphorus block is placed in NMP solvent for ultrasonic stripping for 30min, and the mass concentration of 10mg mL is obtained -1 A commercial glass fiber (GF/A type, diameter 14 mm) diaphragm was placed in the dispersion for 30 minutes with continued ultrasonic treatment, the diaphragm was taken out and dried in a vacuum oven at 60℃for 12 hours to obtain diaphragm #1, and the physical diagram is shown in FIG. 1. The black phosphorus load is 1.78mg/cm 2 The scanning electron microscope and the X-ray energy spectrum are shown in figure 2, which proves that the black phosphorus is uniformly distributed on the diaphragm fiber.
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
Application of diaphragm
1. Zinc-zinc symmetrical battery
The obtained composite membrane is used as a zinc ion battery membrane, and 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, a button cell is assembled by using the zinc foil as a counter electrode, constant-current charge and discharge tests are carried out, and the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 . The voltage-time curve is shown in fig. 3, and after 3500 hours of cycle, the battery still has no short circuit phenomenon, and the short circuit time exceeds 3500 hours.
2. Zinc-hydrated vanadium pentoxide full cell
The obtained composite membrane is used as a zinc ion battery membrane, and 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, constant-current discharge test is carried out, and the current density is 2A g -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The cycle performance is shown in FIG. 4, and it can be seen that the initial discharge capacity of the battery is 203mAh g -1 The capacity retention after 1500 cycles was 90%.
Example 2
Preparation of black phosphorus modified glass fiber diaphragm #2 and application of black phosphorus modified glass fiber diaphragm #2 in water-based zinc battery
The black phosphorus block is placed in NMP solvent for ultrasonic stripping for 30min to obtain the mass concentration of 5mg mL -1 Commercial glass fiber (GF/A type, diameter 14 mm) membrane was placed in the dispersion for 30 minutes of ultrasonic treatment, and the resulting membrane was dried in a vacuum oven at 60℃for 12 hours to give membrane #2 with a black phosphorus loading of 0.76mg/cm 2 。
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
The application process comprises the following steps:
1. zinc-zinc symmetrical battery
The obtained composite membrane is used as a zinc ion battery membrane, and 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, a button cell is assembled by using the zinc foil as a counter electrode, constant-current charge and discharge tests are carried out, and the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 The short-circuit time was 1534 hours, which was reduced compared to example 1.
2. Zinc-hydrated vanadium pentoxide full cell
The obtained composite membrane is used as a zinc ion battery membrane, and 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, constant-current discharge test is carried out, and the current density is 2A g -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The first discharge capacity of the battery is 192mAh g -1 The capacity retention after 1500 cycles was 81% with a slight decrease compared to example 1 due to the lower black phosphorus loading.
Example 3
Preparation of black phosphorus modified glass fiber diaphragm #3 and application of black phosphorus modified glass fiber diaphragm #3 in water-based zinc battery
The black phosphorus block is placed in NMP solvent for ultrasonic stripping for 30min, and the mass concentration of 10mg mL is obtained -1 Commercial glass fiber (GF/A type, diameter 14 mm) membrane was placed in the dispersion for 30 minutes of ultrasonic treatment, and the resulting membrane was dried in a vacuum oven at 60℃for 12 hours to give membrane #1 with a black phosphorus loading of 1.78mg/cm 2 。
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
The application process comprises the following steps:
1. zinc-zinc symmetrical battery
Using the obtained composite separator #1 as a zinc ion battery separator, 5mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, a button cell is assembled by using the zinc foil as a counter electrode, constant-current charge and discharge tests are carried out, and the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 The short-circuit time was 2232 hours.
2. Zinc-hydrated vanadium pentoxide full cell
The obtained composite membrane is used as a zinc ion battery membrane, and 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, constant-current discharge test is carried out, and the current density is 2A g -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The first discharge capacity of the battery is 191mAh g -1 The capacity retention after 1500 cycles was 77%.
Comparative example 1
Preparation of unmodified glass fiber diaphragm and application of unmodified glass fiber diaphragm in water-based zinc battery
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
1. Zinc-zinc symmetrical battery
Commercial glass fiber (GF/A model, diameter 14 mm) was used as a zinc ion battery separator, and its physical diagram is shown in FIG. 5, and the scanning electron microscope diagram is shown in FIG. 6. 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, a button cell is assembled by using the zinc foil as a counter electrode, constant-current charge and discharge tests are carried out, and the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 . As shown in fig. 7, the short-circuit time was 359 hours.
2. Zinc-hydrated vanadium pentoxide full cell
Commercial glass fiber (GF/A model, diameter 14 mm) was used as zinc ion battery separator, 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, constant-current discharge test is carried out, and the current density is 2A g -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The first discharge capacity of the battery is 182mAh g -1 The capacity retention after 1500 cycles was 49%.
Comparative example 2
Preparation of unmodified glass fiber diaphragm and application of unmodified glass fiber diaphragm in water-based zinc battery
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
Zinc metal plates were placed in 20mM H 3 PO 4 The zinc sheet with zinc phosphate rich surface was obtained by soaking in the aqueous solution for 2 hours, and the time-of-flight secondary ion mass spectrum ((TOF-SIMS)) is shown in FIG. 8. a is the surface PO of the zinc sheet 4 And b is a corresponding side view.
1. Zinc-zinc symmetrical battery
Glass to be commercializedFiber (GF/A model, diameter 14 mm) as zinc ion battery separator, 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; the zinc sheet is used as a negative electrode, the button cell is assembled by using the zinc sheet as a counter electrode, and constant current charge and discharge tests are carried out, wherein the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 As shown in fig. 9, the short-circuit time was 744 hours.
2. Zinc-hydrated vanadium pentoxide full cell
Commercial glass fiber (GF/A model, diameter 14 mm) was used as zinc ion battery separator, 2mol L -1 ZnSO of (2) 4 The aqueous solution is used as electrolyte; the zinc sheet is used as a negative electrode, the hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, and constant current charge and discharge tests are carried out, wherein the current density is 2A g -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The first discharge capacity of the battery is 185mAh g -1 The capacity retention after 1500 cycles was 71%.
Comparative example 3
Preparation of unmodified glass fiber diaphragm and application of unmodified glass fiber diaphragm in water-based zinc battery
Vanadium pentoxide powder (3.64 g) and 30% hydrogen peroxide (16 mL) were added to 200mL deionized water. After 24 hours of aging, the resulting hydrated vanadium pentoxide precipitate was collected, washed and freeze-dried for 12 hours. Hydrated vanadium pentoxide powder with polyvinylidene fluoride (PVDF) according to 9:1 by mass ratio. The mixture was then dispersed in NMP solvent. And coating the mixed slurry on carbon paper and drying the carbon paper in a vacuum oven at 60 ℃ for 12 hours to obtain the hydrated vanadium pentoxide anode.
1. Zinc-zinc symmetrical battery
Commercial glass fiber (GF/A model, diameter 14 mm) was used as zinc ion battery separator, 2mol L -1 ZnSO of (2) 4 +20mM H 3 PO 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, a button cell is assembled by using the zinc foil as a counter electrode, constant-current charge and discharge tests are carried out, and the current density is 5mA cm -2 Cut-off capacity of 1mA cm -2 As shown in fig. 10, the short-circuit time was 768 hours. Visible direct on-electricityThe addition of phosphoric acid to the solution does not work effectively.
2. Zinc-hydrated vanadium pentoxide full cell
Commercial glass fiber (GF/A model, diameter 14 mm) was used as zinc ion battery separator, 2mol L -1 ZnSO of (2) 4 +20mM H 3 PO 4 The aqueous solution is used as electrolyte; zinc foil is used as a negative electrode, hydrated vanadium pentoxide is used as a positive electrode to assemble a button cell, constant-current discharge test is carried out, and the current density is 2Ag -1 The voltage interval is 0.6-1.6V (based on the mass of hydrated vanadium pentoxide). The first discharge capacity of the battery is 187mAh g -1 The capacity retention after 1500 cycles was 74%.
Appearance observation of zinc cathode after application
When the morphology of the zinc anode of example 1 and comparative example 1, which was used for 100 hours in the cycle, was observed, the surface morphology was as shown in fig. 11 and 12, and it was found that the dendrites on the surface were significantly reduced after the cycle of the zinc anode in example 1, compared to comparative example 1, which was also the reason for the prolonged short-circuiting time. The battery diaphragm prepared by the invention is applied to a zinc-zinc symmetrical battery, can effectively provide a protection effect for a zinc cathode and inhibit dendrite growth.
The morphology of the zinc negative electrodes after 300 hours of cycling of the symmetric cells of example 1, comparative example 2 and comparative example 3 was observed, the morphology surface was shown in fig. 13, and the cross section was shown in fig. 14, wherein (a) example 1, (b) comparative example 2, (c) comparative example 3, showed a significant reduction in surface dendrites after cycling of the zinc negative electrode compared to the initial zinc phosphate modification of the negative electrode of comparative example 2 and the introduction of phosphoric acid into the electrolyte of comparative example 3, indicating the effectiveness of this strategy.
Example 4
Placing a black phosphorus block in 2M ZnSO 4 The hydrolysis of black phosphorus was observed for 20 days and 60 days in the aqueous solution, and the ionic conductivity in the electrolyte was tested, and the results are shown in fig. 15, which show that black phosphorus can be continuously hydrolyzed in a 2m ZnSO4 aqueous solution to generate phosphoric acid substances. This also shows that after 20 days or 60 days, the black phosphorus block can still release phosphate ions continuously, thereby achieving the purpose of improving the cycle stability of the zinc cathode.
Claims (10)
1. The preparation method of the black phosphorus modified composite membrane for the water-based zinc ion battery is characterized by comprising the following steps: and (3) placing the black phosphorus in the solution, carrying out ultrasonic stripping to obtain black phosphorus dispersion liquid, placing the battery diaphragm in the black phosphorus dispersion liquid, carrying out ultrasonic treatment on the battery diaphragm, taking out the battery diaphragm, and drying to obtain the black phosphorus modified composite diaphragm.
2. The method for preparing the black phosphorus modified composite membrane for the water-based zinc ion battery, which is disclosed in claim 1, is characterized in that the black phosphorus ultrasonic stripping time is more than 30min.
3. The method for preparing a black phosphorus modified composite membrane for an aqueous zinc ion battery according to claim 1, wherein the ultrasonic time of the battery membrane in the black phosphorus dispersion is 15-30min.
4. The method for preparing a black phosphorus modified composite separator for an aqueous zinc-ion battery according to claim 1, wherein the solution comprises a mixed solution of one or more of water, ethanol, NMP, IPA, DMF, DMSO;
and/or the battery separator comprises a composite membrane of any one or more of a glass fiber membrane, a polyolefin membrane, a cellulose membrane, and a Nafion membrane.
5. The method for preparing a black phosphorus modified composite membrane for an aqueous zinc ion battery according to claim 1, wherein the mass concentration of black phosphorus in the black phosphorus dispersion liquid is 5-20mg mL -1 ；
And/or the loading amount of black phosphorus in the black phosphorus modified composite membrane is 0.6-2.5mg cm -2 。
6. The method for preparing a black phosphorus modified composite membrane for an aqueous zinc ion battery according to claim 1, wherein the drying condition is 50-80 ℃ for 6-18h.
7. A black phosphorus-modified composite separator manufactured by the manufacturing method according to any one of claims 1 to 6.
8. The use of the black phosphorus modified composite separator according to claim 7 in an aqueous zinc ion battery.
9. A zinc-hydrated vanadium pentoxide full cell, characterized in that the black phosphorus modified composite membrane of claim 7 is used as a cell membrane, zinc salt aqueous solution is used as electrolyte, zinc foil is used as a negative electrode and a counter electrode, and hydrated vanadium pentoxide is used as a positive electrode.
10. The zinc-hydrated vanadium pentoxide full cell of claim 9 wherein the molar concentration of zinc salt in the aqueous electrolyte is 2-3mol L -1 。
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