CN117673341A - Zinc nickelate and rechargeable zinc ion battery containing zinc nickelate - Google Patents
Zinc nickelate and rechargeable zinc ion battery containing zinc nickelate Download PDFInfo
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- CN117673341A CN117673341A CN202311673108.2A CN202311673108A CN117673341A CN 117673341 A CN117673341 A CN 117673341A CN 202311673108 A CN202311673108 A CN 202311673108A CN 117673341 A CN117673341 A CN 117673341A
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- Prior art keywords
- zinc
- nickelate
- ion battery
- rechargeable
- negative electrode
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011701 zinc Substances 0.000 title claims abstract description 99
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 97
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 32
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 6
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 claims 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011245 gel electrolyte Substances 0.000 abstract description 2
- 239000011244 liquid electrolyte Substances 0.000 abstract description 2
- 229940078494 nickel acetate Drugs 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 2
- XRFJZINEJXCFNW-UHFFFAOYSA-N [Zn+2].[O-][Mn]([O-])(=O)=O Chemical compound [Zn+2].[O-][Mn]([O-])(=O)=O XRFJZINEJXCFNW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses zinc nickelate and a rechargeable zinc ion battery containing zinc nickelate, wherein the preparation method of a zinc nickelate material comprises the steps of mixing zinc nitrate and nickel acetate in any molar ratio to prepare an aqueous solution, reacting the mixed aqueous solution at 200 ℃, washing a precipitate with water, and filtering to obtain the zinc nickelate material. A rechargeable zinc ion battery taking zinc nickelate as a positive electrode: the positive electrode is made of zinc nickelate material, the negative electrode is made of zinc element, the electrolyte is zinc soluble salt as solute, water as solvent and liquid or gel electrolyte with ion conductivity, and the rechargeable battery is formed. The patent is characterized by providing a simple preparation method of the zinc nickelate material, and using zinc nickelate as the positive electrode of the zinc ion battery, so that the problem of manganese dissolution of the manganese oxide positive electrode in the conventional zinc ion battery is avoided.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to zinc nickelate and a rechargeable zinc ion battery containing zinc nickelate.
Background
Compared with a primary battery, the secondary battery can repeatedly perform charge and discharge cycles, and raw materials can be fully utilized, so that the secondary battery is more economical and practical.
Chinese patent CN 101540417a discloses for the first time a rechargeable zinc ion battery with manganese dioxide as positive electrode, zinc as negative electrode, and zinc ion containing solution as electrolyte, in which the zinc ions are stripped from the manganese dioxide through the electrolyte and deposited on the negative electrode during charging, and the above-mentioned processes are just opposite during discharging.
The mechanism of electron storage of the zinc ion battery is as follows:
and (3) a positive electrode:
and (3) a negative electrode:
the reversible deintercalation behavior of zinc ions in the anode material is utilized, so that the battery capable of being charged with zinc ions has the characteristics of high capacity, long cycle life and the like. The zinc ion battery can be widely applied to the fields of personal digital notepads, blectronic Organizers, mobile phones, cordless phones, BP sets, electric toys, game machines, portable data terminals, personal audio-video devices, experimental devices, palm computers and the like.
However, the zinc ion battery using manganese oxide as the positive electrode has a certain disadvantage that the manganese oxide such as manganese dioxide is unstable in structure during charge and discharge, manganese in the positive electrode material is dissolved into an electrolyte to become tetravalent manganese ions during discharge, and manganese ions in the electrolyte are deposited on the surface of the positive electrode during charge, which causes capacity loss in the battery cycle, with the result that the battery cycle life is reduced and volume expansion of the positive electrode is caused by deposition of manganese on the surface of the positive electrode. In order to solve the problem of poor stability of the positive electrode material of the zinc ion battery, the novel material with stable structure is found to be a good method, and the problem of manganese dissolution commonly existing in manganese oxide is avoided by using the zinc nickelate with stable structure as the positive electrode of the zinc ion battery in order to solve the problem of the structural stability of the positive electrode material of the zinc ion battery.
Disclosure of Invention
In the prior art, the manganese dissolution problem of the manganese oxide positive electrode of the zinc ion battery taking manganese dioxide as the positive electrode can occur, so that the positive electrode can cause collapse of the crystal structure of the positive electrode, volume expansion and depletion of electrolyte in the charge and discharge process. In order to solve the problems, the invention discloses zinc nickelate and a rechargeable zinc ion battery containing the zinc nickelate, wherein the rechargeable zinc ion battery taking the zinc nickelate as an anode active material uses a zinc-nickel compound with stable structure as an anode, and nickelate can avoid manganese dissolution.
The invention discovers reversible deintercalation behavior of zinc ions in zinc-nickel compounds, and is realized by the following technical scheme:
the invention discloses a zinc nickelate, which comprises a zinc-nickel compound material mainly comprising nickel, zinc and oxygen and a hydrate thereof, wherein the preparation method of the zinc nickelate comprises the following steps: zinc nitrate and zinc acetate are mixed according to any mole ratio to prepare aqueous solution, and the aqueous solution reacts at 200 ℃ to obtain zinc nickelate.
As a further improvement, the battery of the present invention comprises a positive electrode, a negative electrode, a separator interposed therebetween, and an electrolyte containing anions and cations and having ion conductivity, wherein the positive electrode active material is a zinc nickelate material, the negative electrode is an active material mainly containing zinc, and the electrolyte is a liquid or gel state material mainly containing a soluble salt of zinc as a solute, water or an organic substance as a solvent and having ion conductivity.
As a further improvement, the negative electrode according to the invention is pure metallic zinc or an alloy of zinc.
As a further improvement, the negative electrode comprises a current collector and a negative electrode film on the current collector, wherein the negative electrode film is a paste or film material prepared from an active material, a corrosion inhibitor, a conductive agent and a binder.
As a further improvement, the active material of the invention is formed by mixing one or more zinc-containing materials such as zinc powder, zinc oxide, zinc hydroxide and the like.
As a further improvement, the corrosion inhibitor is used for inhibiting or eliminating hydrogen evolution reaction of zinc element, preferably indium oxide, indium hydroxide or metallic copper, and the addition amount of the corrosion inhibitor is less than 1% of the mass of the anode film.
As a further improvement, the conductive agent of the present invention is preferably graphite, carbon black, acetylene black, carbon fiber or carbon nanotube, and the addition amount of the electron conductive agent is 50% or less of the mass of the negative electrode film.
As a further improvement, the soluble salt of zinc according to the present invention is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc triflate, zinc bromide, zinc iodide, zinc permanganate and zinc bistrifluoromethylsulfonimide.
The beneficial effects of the invention are as follows:
the invention discloses a preparation method of a zinc nickelate material and a rechargeable zinc ion battery taking the zinc nickelate material as an anode. The preparation method of the zinc nickelate material comprises the following steps: mixing zinc nitrate and nickel acetate in any molar ratio to prepare an aqueous solution, reacting the mixed aqueous solution at 200 ℃, washing the precipitate with water and filtering to obtain the zinc nickelate material. A rechargeable zinc ion battery taking zinc nickelate as a positive electrode: the positive electrode is made of zinc nickelate material, the negative electrode is made of zinc element, the electrolyte is zinc soluble salt as solute, water as solvent and liquid or gel electrolyte with ion conductivity, and the rechargeable battery is formed. The patent is characterized by providing a simple preparation method of the zinc nickelate material, and using zinc nickelate as the positive electrode of the zinc ion battery, so that the problem of manganese dissolution of the manganese oxide positive electrode in the conventional zinc ion battery is avoided.
Experiments prove that the rechargeable zinc ion battery has excellent multiplying power performance, reversibility performance and cycle performance. Because the zinc nickelate is more stable in structure in circulation, volume expansion and shrinkage can not occur, and the zinc ion battery using the positive electrode is stable in volume, and is easier to be applied to a mobile power supply such as an automobile starting and stopping battery or an electric bicycle battery than the existing manganese oxide zinc battery. In addition, as the zinc nickelate does not contain manganese, the zinc nickelate does not dissolve manganese to consume electrolyte, and the electrolyte of the battery is exhausted, so that the zinc nickelate battery is more stable in cycle and is more suitable for being used as an energy storage battery than the existing manganese oxide zinc battery.
Drawings
FIG. 1 is a scanning microscope photograph of zinc nickelate compound ZnNiO-1 prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the zinc nickelate compound ZnNiO-1 prepared in example 1;
FIG. 3 is a scanning microscope photograph of zinc nickelate compound ZnNiO-2 prepared in example 2;
FIG. 4 is an X-ray diffraction pattern of the zinc nickelate compound ZnNiO-2 prepared in example 2;
FIG. 5 is a charge-discharge curve of a zinc ion battery Cell-1 in which a zinc nickelate compound ZnNiO-1 prepared in example 1 is used as a positive electrode active material;
fig. 6 is a charge-discharge curve of a zinc ion battery Cell-2 in which the zinc nickelate compound ZnNiO-2 prepared in example 2 is a positive electrode active material.
Detailed Description
The invention discloses zinc nickelate and a rechargeable zinc ion battery containing zinc nickelate, and the technical scheme for preparing the zinc nickelate is as follows: mixing zinc nitrate and zinc acetate according to any mole ratio to prepare aqueous solution, reacting the aqueous solution at 200 ℃, filtering solid precipitate in the solution, washing with water and drying to obtain the zinc nickelate material.
The zinc nickelate material is a zinc-nickel compound material mainly comprising nickel, zinc and oxygen.
The invention aims to provide a novel rechargeable zinc ion battery with a positive electrode.
A chargeable zinc ion battery is composed of a positive electrode, a negative electrode, a separation film between the positive electrode and the negative electrode and an electrolyte containing anions and cations and having ion conductivity, wherein the negative electrode adopts an active material mainly containing zinc element; the positive electrode active material is a zinc nickelate material; the electrolyte is a liquid or gel material having ionic conductivity with zinc soluble salt as a solute and water as a solvent.
The negative electrode can be pure metal zinc or zinc alloy, and the following scheme can be adopted: the negative electrode comprises a current collector and a negative electrode film on the current collector, wherein the negative electrode film is a paste or film material prepared from an active material, a corrosion inhibitor, a conductive agent and a binder, the active material is formed by mixing one or more zinc-containing materials such as zinc powder, zinc oxide, zinc hydroxide and the like, and the binder can be polytetrafluoroethylene, water-soluble rubber, polyvinylidene fluoride or cellulose. Wherein the corrosion inhibitor is used for inhibiting or eliminating hydrogen evolution reaction of zinc element, preferably indium oxide, indium hydroxide or metallic copper, and the addition amount of the corrosion inhibitor is less than 1% of the mass of the anode film. Wherein the electron conductive agent is preferably graphite, carbon black, acetylene black, carbon fiber or carbon nano tube, and the addition amount of the electron conductive agent is less than 50% of the mass of the cathode film.
The positive electrode is formed by a positive electrode film on a current collector and a current collector, the positive electrode film is a paste or film material prepared from zinc nickelate active substance, an electronic conductive agent and a binder, wherein the electronic conductive agent is graphite, carbon black, acetylene black, carbon fiber or carbon nano tube, and the addition amount is less than 50% of the mass of the positive electrode film; the binder is polytetrafluoroethylene, water-soluble rubber, polyvinylidene fluoride or cellulose, and the addition amount is less than 20% of the mass of the positive electrode film.
The soluble salt of zinc is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc triflate, zinc bromide, zinc iodide, zinc permanganate and zinc bistrifluoromethylsulfonimide. The pH of the electrolyte may be adjusted to 3 to 7 by adding an acid, a base, a buffer solution, or the like.
The rechargeable zinc ion battery can be made into a button type, a cylindrical type or a square type structure.
The technical scheme of the invention is further described by the following specific embodiments and the accompanying drawings in the specification:
example 1:
zinc nitrate Zn (NO) 3 ) 2 And zinc acetate Ni (AC) 2 The molar ratio is 2:1 preparing into aqueous solution, reacting 500mL of the aqueous solution in water bath at 85deg.C for 72 hours, filtering the reacted precipitate, repeatedly washing with distilled water for more than 3 times, and oven drying the filtrate to obtain the final productZinc nickelate, designated ZnNiO-1, can be produced. A scanning microscope picture of ZnNiO-1 is shown in FIG. 1, the zinc nickelate compound is in a short rod shape, an X-ray diffraction picture of ZnNiO-1 is shown in FIG. 2, and the presence of zinc nickelate (ZnNi) is analyzed by an object image 2 O 4 ) Characteristic peaks (111) and (220) of the compound, the material being a nickel zinc oxide compound containing a zinc nickelate phase.
Example 2:
zinc nitrate Zn (NO) 3 ) 2 And zinc acetate Ni (AC) 2 The molar ratio is 1:1 preparing into aqueous solution, putting 500mL of the aqueous solution into a high-pressure reaction kettle, reacting for 72 hours at 85 ℃, filtering the reacted precipitate, repeatedly washing with distilled water for more than 3 times, and drying the filtrate in an oven to obtain zinc nickelate, wherein the zinc nickelate is ZnNiO-2. As shown in FIG. 3, the scanning microscope image of ZnNiO-2 shows a disk shape, the diameter is about 500nm, the thickness is several nanometers, the X-ray diffraction image of ZnNiO-2 shows FIG. 4, and the zinc nickelate (ZnNi 2 O 4 ) Characteristic peaks (111) and (220) of the compound, the material being a nickel zinc oxide compound containing a zinc nickelate phase.
Example 3
The ZnNiO-1, the conductive agent acetylene black and the adhesive are coated on a stainless steel foil in a ratio of 7:2:1, cut into a certain size, and dried in vacuum to obtain the zinc manganate ZnNiO-1 electrode slice.
ZnNiO-1 electrode slice is taken as an anode, zinc foil (0.1 mm thick) is taken as a cathode, and electrolyte is 1mol L -1 ZnSO 4 The aqueous solution was assembled into a rechargeable zinc ion battery, designated Cell-1.Cell-1 Cell at 50mAg -1 The multiple charge-discharge cycle curve at constant current is shown in fig. 5.
Example 4:
and (3) coating ZnNiO-2, an electroconductive agent acetylene black and a binder on the stainless steel foil in a ratio of 7:2:1, cutting into a certain size, and drying in vacuum to obtain the ZnNiO-2 electrode slice.
The zinc powder electrode is prepared as follows: the zinc powder, the conductive agent acetylene black and the adhesive are mixed according to the mass ratio of 40:50:10, pressing the mixture on a stainless steel net, cutting the mixture into a certain size, and drying the mixture in vacuum.
The ZnNiO-2 electrode plate is used as an anode, the zinc powder electrode is used as a cathode, the mass of zinc powder is ten times that of ZnNiO-2 material, and the electrolyte is 0.1mol L -1 ZnSO 4 The aqueous solution was assembled into a rechargeable zinc ion battery, designated Cell-2.Cell-2 Cell at 50mAg -1 The multiple charge-discharge cycle curve at constant current is shown in fig. 6.
The foregoing is not intended to limit the invention, and it should be noted that variations, modifications, additions and substitutions are possible, without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (8)
1. The zinc nickelate is characterized by comprising a zinc-nickel compound material mainly comprising nickel, zinc and oxygen and a hydrate thereof, wherein the preparation method of the zinc nickelate comprises the following steps of: zinc nitrate and zinc acetate are mixed according to any mole ratio to prepare aqueous solution, and the aqueous solution reacts at 200 ℃ to obtain zinc nickelate.
2. The rechargeable zinc ion battery containing zinc nickelate is characterized by comprising a positive electrode, a negative electrode, a separation membrane between the positive electrode and the negative electrode and electrolyte containing anions and cations and having ion conductivity, wherein the positive electrode active material is a zinc nickelate material, the negative electrode adopts an active material taking zinc element as a main component, and the electrolyte is a liquid or gel state material taking zinc soluble salt as a solute, water or an organic matter as a solvent and having ion conductivity.
3. The zinc-acid-zinc-containing rechargeable zinc-ion battery of claim 2, wherein said negative electrode is pure metallic zinc or zinc alloy.
4. The rechargeable zinc ion battery of claim 2 wherein said negative electrode comprises a current collector and a negative electrode film on the current collector, the negative electrode film being a paste or film material made of an active material, a corrosion inhibitor, a conductive agent and a binder.
5. The rechargeable zinc ion battery of claim 4 wherein said active material is formed by mixing one or more zinc containing materials such as zinc powder, zinc oxide, zinc hydroxide, and the like.
6. The rechargeable zinc ion battery containing zinc nickelate according to claim 4, wherein the corrosion inhibitor is used for inhibiting or eliminating hydrogen evolution reaction of zinc element, preferably indium oxide, indium hydroxide or metallic copper, and the addition amount of the corrosion inhibitor is less than 1% of the mass of the negative electrode film.
7. The rechargeable zinc ion battery containing zinc nickelate according to claim 4, wherein the conductive agent is preferably graphite, carbon black, acetylene black, carbon fiber or carbon nanotube, and the addition amount of the electron conductive agent is less than 50% of the mass of the negative electrode film.
8. The zinc-acid zinc-containing rechargeable zinc ion battery of claim 2 or 3 or 4 or 5 or 6 or 7 wherein the soluble salt of zinc is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc triflate, zinc bromide, zinc iodide, zinc permanganate, and zinc bis (trifluoromethylsulfonyl) imide.
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