CN116914283A - Water-based organic hybridization secondary calcium ion battery for forming calcium alloy negative electrode based on electrochemistry and application thereof - Google Patents
Water-based organic hybridization secondary calcium ion battery for forming calcium alloy negative electrode based on electrochemistry and application thereof Download PDFInfo
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000882 Ca alloy Inorganic materials 0.000 title claims abstract description 36
- 238000009396 hybridization Methods 0.000 title claims abstract description 14
- 230000005518 electrochemistry Effects 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000003792 electrolyte Substances 0.000 claims abstract description 54
- 239000011575 calcium Substances 0.000 claims abstract description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 35
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical group [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 claims abstract description 19
- 229960003351 prussian blue Drugs 0.000 claims abstract description 19
- 239000013225 prussian blue Substances 0.000 claims abstract description 19
- 239000011149 active material Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 34
- 239000011888 foil Substances 0.000 claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- PUQLFUHLKNBKQQ-UHFFFAOYSA-L calcium;trifluoromethanesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PUQLFUHLKNBKQQ-UHFFFAOYSA-L 0.000 claims description 6
- -1 calcium tetrafluoroborate Chemical compound 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- WFABOCFDABTAPE-UHFFFAOYSA-N calcium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ca+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 WFABOCFDABTAPE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000002161 passivation Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- 229910001297 Zn alloy Inorganic materials 0.000 description 22
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
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- 229910045601 alloy Inorganic materials 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000007773 negative electrode material Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of calcium ion batteries, and discloses a water system organic hybridization secondary calcium ion battery for forming a calcium alloy negative electrode based on electrochemistry and application thereof. The water-based organic hybridization secondary calcium ion battery comprises a battery cathode, electrolyte, a diaphragm and a battery anode, wherein the battery cathode is a calcium alloy cathode; the electrolyte is water system-organic hybridized calcium ion electrolyte; the active material of the positive electrode is Prussian blue active material; the water system-organic hybridized calcium ion electrolyte is prepared by mixing and dissolving an organic solvent, calcium salt and deionized water, and fully stirring. The in-situ prepared calcium alloy cathode of the calcium ion battery remarkably improves the deposition stripping reversibility of calcium ions in electrolyte, reduces the passivation reaction of calcium metal, and the prepared secondary calcium ion battery shows the advantages of more excellent high-voltage platform and long cycle life. Meanwhile, the electrode and the electrolyte are cheap and easy to obtain, the preparation cost is low, the time is short, the safety and the environmental protection are realized, and the application prospect is good.
Description
Technical Field
The invention belongs to the technical field of calcium ion batteries, and particularly relates to a water-based organic hybridization secondary calcium ion battery for forming a calcium alloy negative electrode based on electrochemistry and application thereof.
Background
Energy is a constant topic in human society. Lithium ion batteries have achieved tremendous success in powering electric vehicles and portable electronic products over the past several decades. With the increasing demand for electrochemical energy storage systems for smart grids and electrified transportation applications, raw material supply issues have raised concerns. Considering the limited and maldistribution of lithium resources, multivalent ion batteries are currently considered very promising in the search for new batteries with sustainability and economy. Among them, the calcium ion battery is widely focused because the oxidation-reduction potential of calcium metal is low (-2.9 v vs. she), the abundance of calcium element is high (4.1% in crust), 2500 times more than lithium, green, environment-friendly and nontoxic.
At present, the development of the calcium ion battery is still in the preliminary stage, and no matter the type of the positive electrode material or the negative electrode material or the electrolyte, the development of the material with high capacity, good cycle performance and good electrochemical stability is needed. In particular, the calcium metal negative electrode in the calcium ion battery has a serious passivation problem. Compared with Li or Na metal, ca metal cathode is not easy to form dendrite, and is expected to improve the safety of the battery. However, divalent calcium ions and active calcium metal, positive electrode material, nonaqueous electrolyte solution undergo strong interactions, resulting in high charge transfer barriers at the electrode-electrolyte interface, and thus in low electrochemical performance of the battery. Therefore, further research on interfacial chemistry and design of suitable electrode-electrolyte interfaces, i.e. design of mutually compatible calcium negative electrode and calcium salt electrolyte, and high-performance positive electrode highly adapted thereto, lowering of the charge transfer barrier at the electrode-electrolyte interface is crucial for achieving high-performance calcium ion batteries.
Disclosure of Invention
The invention aims to solve the defects and the shortcomings of the prior art, and the primary aim is to provide a water-based organic hybridization secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode, which can effectively improve the problem of high charge transfer barrier at an electrode-electrolyte interface, so as to solve the problems of low voltage, poor cycle performance and high cost of the secondary calcium ion battery in the prior art.
It is another object of the present invention to provide the use of the above-described secondary calcium ion battery.
The aim of the invention is achieved by the following technical scheme:
the water-based organic hybridization secondary calcium ion battery based on electrochemical formation of the calcium alloy negative electrode comprises a battery negative electrode, electrolyte, a diaphragm and a battery positive electrode, wherein the battery negative electrode is the calcium alloy negative electrode; the electrolyte is a water system-organic hybridized calcium ion electrolyte; the active material of the battery anode is Prussian blue active material; the water system-organic hybridized calcium ion electrolyte is prepared by mixing and dissolving an organic solvent, calcium salt and deionized water, and fully stirring.
Preferably, the calcium alloy cathode is prepared by polishing a metal foil to remove a surface oxide layer, then soaking the polished metal foil with dilute acid to remove a residual oxide layer, and finally cleaning the polished metal foil with deionized water and absolute ethyl alcohol to obtain the metal foil with the surface oxide layer removed; cutting the metal foil with the oxide layer removed, taking the metal foil cut piece as a positive electrode and a negative electrode of the symmetrical battery, taking a water system-organic hybridization calcium ion electrolyte as the electrolyte, assembling the battery into a CR2032 button battery, and disassembling the battery after charge-discharge circulation; or directly using a metal foil which is alloyed with calcium ions as a negative electrode current collector, and forming the calcium alloy in situ by the metal foil after the battery is assembled.
More preferably, the metal foil is zinc foil, tin foil, nickel foil, molybdenum foil, copper foil, or manganese foil.
More preferably, the dilute acid is dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid, and the concentration of the dilute acid is 0.5-2 mol/L.
Preferably, the organic solvent is one or more of nitrile organic solvent, ether organic solvent and ester organic solvent.
More preferably, the nitrile organic solvent is more than one of acetonitrile, succinonitrile or adiponitrile; the ether organic solvent is ethylene glycol dimethyl ether or/and triethylene glycol dimethyl ether; the ester organic solvent is at least one of propylene carbonate, ethylene carbonate and diethyl carbonate.
Preferably, the calcium salt is more than one of calcium triflate, calcium bis (trifluoromethylsulfonyl) imide, calcium bisfluorosulfonyl imide, calcium perchlorate, calcium tetrafluoroborate, calcium hexafluorophosphate, calcium nitrate, calcium fluoride and calcium chloride.
Preferably, the Prussian blue active material is nickel manganese Prussian blue, copper Prussian blue or cobalt Prussian blue. The Prussian blue positive electrode active material can be prepared rapidly by adopting common methods in industry, such as a common coprecipitation method, a hydrothermal synthesis method and a ball milling method.
And dissolving and pulping the Prussian blue active material, the conductive carbon and the binder by using a solvent to obtain slurry, coating the slurry on a current collector, drying in vacuum, and cutting to obtain the required size to obtain the battery anode.
Preferably, the molar ratio of the organic solvent to the calcium salt to the deionized water is 1 (10-30): 10-30.
The secondary calcium ion battery is applied to energy storage equipment or electric equipment.
The secondary calcium ion battery comprises a metal foil anode for preparing a calcium alloy anode, a water-based organic hybridization electrolyte and a Prussian blue anode. The positive electrode comprises a positive electrode active material layer and a positive electrode current collector, wherein the positive electrode active material layer comprises conductive carbon, a binder and the positive electrode active material. The conductive carbon and the binder can be any carbon material with conductive performance known to those skilled in the battery field, and any material with active material adhered to and compounded on the current collector, preferably polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, polyvinyl alcohol and the like. The current collector can be any current collector which can be recognized by a person skilled in the battery field, and is preferably graphite paper or stainless steel mesh. The content of the conductive carbon in the positive electrode material is preferably 10 to 15%, the content of the binder in the positive electrode material is preferably 10 to 15%, and the preferred content of the positive electrode active material is 70 to 80%. The calcium alloy cathode is directly generated in electrochemical charge-discharge reaction, so that the metal foil can be directly used as a cathode current collector when the secondary calcium ion battery is prepared.
Compared with the prior art, the invention has the following beneficial effects:
1. the in-situ prepared calcium alloy cathode of the calcium ion battery remarkably improves the deposition stripping reversibility of calcium ions in electrolyte, reduces the passivation reaction of calcium metal, and the prepared secondary calcium ion battery shows the advantages of more excellent high-voltage platform and long cycle life. The prepared calcium alloy cathode takes a low-cost, safe and harmless metal foil as a substrate for electrochemically preparing the alloy. Compared with the expensive and easily-oxidized calcium metal, the prepared calcium alloy has the advantages of low cost, simple preparation steps and mild and controllable preparation process. Meanwhile, in electrochemical charge and discharge, the calcium alloy can greatly relieve the severe passivation reaction of calcium metal and electrolyte, and improve the reversibility of deposition stripping of calcium ions at the anode-electrolyte interface.
2. The cycle times of the secondary calcium metal battery prepared by the method can reach 400 circles, the voltage platform is up to 1.85V, the electrochemical stability and the working voltage are far superior to those of the calcium metal battery assembled by directly using expensive calcium metal, the raw materials are cheap and easy to obtain, the preparation cost is low, the time is short, the safety and the environmental protection are realized, and the application prospect is good.
3. According to the calcium alloy anode, the metal foil substrate is directly used as an anode current collector, and calcium alloy is formed through in-situ electrochemical reaction in the charging and discharging process of a battery to be used as the anode of a secondary calcium ion battery. The alloy cathode can be directly obtained by an electrochemical method without a complicated preparation process. Compared with the expensive and easily passivated calcium metal anode, the metal foil substrate is directly used as the current collector of the anode, and the anode has the advantages of environmental protection and low cost.
4. The calcium alloy cathode formed by in-situ electrochemistry effectively relieves the problem of calcium metal passivation by utilizing the alloy interface layer, inhibits dendrite growth, and ensures ultra-long-term stable calcium stripping/electroplating; the secondary calcium ion battery using the in-situ formed calcium alloy negative electrode shows excellent discharge voltage, is superior to other calcium ion batteries, and shows extremely remarkable advantages in battery cycle life compared with the secondary calcium ion battery using calcium metal as the negative electrode.
5. The water molecules in the water system-organic hybridization electrolyte play a role in strong lubrication and shielding, and promote large-size Ca 2+ The Prussian blue active material is quickly embedded and separated, so that the diffusion dynamics of the battery anode material is improved; meanwhile, the organic components in the hybrid electrolyte can effectively inhibit the decomposition of water molecules in the electrolyte, widen the electrochemical window of the electrolyte, and slow down the unavoidable passivation reaction of calcium metal on the cathode. The water system-organic hybrid calcium ion electrolyte has high purity, good chemical stability, good compatibility with conventional electrode materials, high ion conductivity and ion mobility, simple preparation method and mild and controllable conditions.
6. In the water system-organic hybridized calcium ion electrolyte prepared by the invention, the strong lubrication and shielding effects of the water solvent obviously promote large-size Ca 2+ Thereby promoting Ca 2+ Mass storage in the Prussian blue positive electrode. At the same time, the components of the organic solvent obviously inhibit H 2 O and reduces the formation of unavoidable calcium metal byproducts. Therefore, the Prussian blue positive electrode shows excellent electrochemical stability and rapid calcium ion diffusion kinetics in the water-organic hybrid electrolyte, and is compatible with a stable calcium alloy negative electrode, so that the prepared secondary calcium ion battery finally shows excellent cycle stability.
Drawings
FIG. 1 is a cross-sectional Scanning Electron Microscope (SEM) photograph of a cathode of an electrochemically prepared calcium-zinc alloy of example 1.
Fig. 2 is an X-ray diffraction pattern (XRD) of the electrochemically prepared calcium-zinc alloy negative electrode and zinc foil of example 1.
FIG. 3 is a selected area electron diffraction pattern (SAED) of the electrochemically prepared calcium zinc alloy negative electrode of example 1.
FIG. 4 is a schematic diagram of example 1The current density of the zinc substrate symmetrical cell on the surface is 0.2mA cm -2 The dough kneading capacity density is 0.2mAh cm -2 The time voltage profile below.
FIG. 5 charge and discharge curves of the assembled secondary calcium ion battery of example 1 at a current density of 0.1A/g
Fig. 6 is a graph of the rate performance of the assembled secondary calcium ion battery of example 1.
FIG. 7 is a graph showing the cycling stability of the assembled secondary calcium ion battery of example 1 at a current density of 1A/g.
FIG. 8 is a graph showing the in-plane current density of 0.2mA cm for the calcium metal symmetrical cell of comparative example 2 -2 The dough kneading capacity density is 0.2mAh cm -2 The time voltage profile below.
FIG. 9 is a charge and discharge curve of the assembled secondary calcium ion battery of comparative example 2 at a current density of 0.1A/g.
Fig. 10 is a graph of the rate performance of the assembled secondary calcium ion battery of comparative example 2.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. Preparation of aqueous-acetonitrile hybrid electrolyte
Mixing and dissolving calcium trifluoromethane sulfonate, acetonitrile as an organic solvent and deionized water in a molar ratio of 1:20:20, and fully stirring for 12 hours to obtain a water system-acetonitrile hybridized calcium ion electrolyte (1-20-20) with good dispersibility.
2. Preparation of electrochemically formed calcium-zinc alloy negative electrode
(1) Taking zinc foil with the thickness of 100 mu m, removing the surface oxide layer, firstly grinding most of the ZnO oxide layer on the surface of the zinc foil by sand paper, then soaking the ground zinc foil in 1mol/L HCl for 1min, and removing the residual ZnO oxide layer.
(2) And (3) taking the zinc foil with the ZnO oxide layer removed as an electrode, taking the water system-acetonitrile hybridized calcium ion electrolyte 1-20-20 as an electrolyte and taking glass fiber as a diaphragm to assemble the CR2032 button cell, so as to prepare the symmetrical cell.
(3) The symmetrical battery assembled in the step (2) is arranged on a constant current charge-discharge tester with the area current density of 0.1-0.3 mAcm -2 The density of the dough kneading capacity is 0.1-0.3 mAh cm -2 And charging and discharging are carried out, and the cycle time is 50-100 h.
(4) Disassembling the symmetrical battery after electrochemical circulation in the step (3), wherein an electrode is a calcium-zinc alloy negative electrode.
The calcium-zinc alloy in the calcium-zinc alloy cathode is formed in situ in the electrochemical charge-discharge process, and can be rapidly prepared and applied to the preparation of various appliance materials.
3. Preparation of nickel-manganese Prussian blue active material
(1) 2g of trisodium citrate dihydrate, 0.539g of NiCl are weighed out 2 ·6H 2 O and 0.278g of Mn (CH) 3 CO 2 ) 2 ·4H 2 O was dissolved in 100mL of deionized water to give solution A.
(2) Weigh 2.06g of Na 4 Fe(CN) 6 ·10H 2 O was dissolved in 100mL of deionized water to give solution B.
(3) And (3) dropwise adding the solution A into the solution B, fully stirring at normal temperature and normal pressure for 24 hours, and aging for 24 hours after stirring is completed. And finally, centrifugally washing the aged solution for 2 times by using deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain the nickel-manganese Prussian blue active material (NiMnPB).
4. Preparation of secondary calcium ion battery
And (3) taking 40mg of the prepared active material NiMnPB and 5mg of conductive carbon black Super-P, fully mixing and grinding for 30min, adding 250mg of polyvinylidene fluoride with mass fraction of 2%, stirring and mixing for 12h to obtain uniform slurry, uniformly coating the slurry on a graphite paper current collector, and carrying out vacuum drying at 80 ℃ for 24h to obtain the NiMnPB positive electrode plate.
And 2, taking 1-20-20 of water system-acetonitrile hybridized calcium ion electrolyte as electrolyte, taking glass fiber as a diaphragm, taking the calcium-zinc alloy prepared in the step 2 as a negative electrode, taking a NiMnPB positive electrode plate as a positive electrode, and assembling to form the CR2032 type button battery, so as to prepare the secondary calcium ion battery.
5. Performance test of secondary calcium ion battery and symmetrical battery
And (3) performing constant-current charge and discharge performance test on the prepared secondary calcium ion battery, wherein the charge cutoff voltage is 2.2V and the discharge cutoff voltage is 0.2V.
FIG. 1 is a cross-sectional Scanning Electron Microscope (SEM) photograph of a cathode of an electrochemically prepared calcium-zinc alloy of example 1. As can be seen from fig. 1, the cross section of the negative electrode of the calcium-zinc alloy is very flat, which indicates that the calcium-zinc alloy has no dendrite growth problem during formation as is common in the lithium ion battery, which ensures that the secondary calcium ion battery cannot cause short circuit of the battery due to dendrite growth problem, and causes serious safety problem. Fig. 2 is an X-ray diffraction pattern (XRD) of the electrochemically prepared calcium-zinc alloy negative electrode and zinc foil of example 1. Analysis by fig. 2 shows that the diffraction angle of the negative electrode of the calcium-zinc alloy is significantly shifted to a lower diffraction angle than that of the zinc foil, which is due to the effect of the calcium-zinc alloy, demonstrating the formation of the calcium-zinc alloy. FIG. 3 is a selected area electron diffraction pattern (SAED) of the electrochemically prepared calcium zinc alloy negative electrode of example 1. The analysis of fig. 3 further demonstrates the successful synthesis of a calcium zinc alloy negative electrode.
FIG. 4 shows the in-plane current density of 0.2mA cm for the symmetrical Ca-Zn alloy cell of example 1 -2 The dough kneading capacity density is 0.2mAh cm -2 The time voltage profile below. As can be seen from fig. 4, the hysteresis voltage of the zinc-substrate symmetric cell is very small (about 0.044V) and can be stably cycled for over 1600 hours, which suggests that the in-situ formed calcium-zinc alloy can effectively lower the charge transfer barrier at the electrode-electrolyte interface, thereby improving the reversibility of calcium ion deposition exfoliation at the electrode-electrolyte interface. Fig. 5 is a charge and discharge curve of the assembled secondary calcium ion battery of example 1 at a current density of 0.1A/g. As can be seen from fig. 5, the secondary calcium ion battery assembled in example 1 also exhibited an excellent high voltage plateau at a current density of 0.1A/g, with a voltage plateau of up to 1.85V and an average discharge voltage of 1.52V. FIG. 6 is a schematic representation of a secondary calcium ion battery assembled in accordance with example 1Rate performance graph. As can be seen from fig. 6, after a large current density of 5A/g cycle, the current density was returned to 0.1A/g, and a capacity of 144mAh/g was still exhibited, and it was found that the secondary calcium ion battery assembled in example 1 was excellent in the rate stability. FIG. 7 is a graph showing the cycling stability of the assembled secondary calcium ion battery of example 1 at a current density of 1A/g. As can be seen from fig. 7, the secondary calcium ion battery assembled in example 1 was stable for a long period of 400 cycles at a current density of 1A/g, and this stability was far superior to the cycling stability of most secondary calcium ion batteries using expensive calcium metal as the negative electrode.
Example 2
In the preparation process of the symmetrical battery and the secondary calcium ion battery in the example 1, all the steps and the materials used are the same except that the molar ratio of the water solvent to the acetonitrile solvent in the water system-acetonitrile hybridized calcium ion electrolyte is different. Example 2 was used with 1:10:30 molar ratio of calcium trifluoromethane sulfonate, acetonitrile and deionized water miscible water system-acetonitrile hybridized calcium ion electrolyte (1-10-30);
example 3
Example 3 aqueous-acetonitrile hybrid calcium ion electrolyte (1-30-10) miscible with calcium trifluoromethane sulfonate, acetonitrile, deionized water used in a molar ratio of 1:30:10;
example 4
The difference from example 1 is that: the negative electrode in the secondary calcium ion battery assembly is a zinc foil with an oxide layer removed, and the zinc foil is used as a negative electrode substrate (current collector) which can generate a calcium-zinc alloy negative electrode in the electrochemical cycle process. The electrochemical properties of the prepared secondary calcium ion battery and the symmetric battery are basically consistent, and the preparation is more convenient and quicker than that of the example 1.
Comparative example 1
Comparative example 1 calcium triflate and acetonitrile miscible calcium ion acetonitrile electrolyte (1-40) at a molar ratio of 1:40 was used.
The symmetrical cells of examples 1-3 and comparative example 1 had an in-plane current density of 0.5mAcm -2 The dough kneading capacity density is 0.5mAh cm -2 Conventional cycle stability tests were performed below, the stability of the symmetrical cells being shown in table 1.
Table 1 stability of symmetrical batteries of examples 1 to 3 and comparative example 1
Table 1 shows the stability of the symmetrical cells of examples 1-3 and comparative example 1. As can be seen from Table 1, the introduction of water molecules into the electrolyte in examples 1-3 compared with comparative example 1 greatly improved the cycle life of the symmetrical cells of examples 1-3 compared with comparative example 1. The method is characterized in that the introduction of water molecules promotes the generation of calcium-zinc alloy on the surface of the electrode, so that calcium ions at the electrode-electrolyte interface can be stably deposited and peeled off, and the cycle life of the symmetrical battery is prolonged. Meanwhile, compared with examples 2 and 3, the symmetrical battery has the longest cycle time, which shows that the stability of the calcium ion deposition stripping in the electrode-electrolyte interface is the best, and the water system-acetonitrile hybridization electrolyte 1-20-20 is the best hybridization electrolyte, so that the charge transfer barrier at the electrode-electrolyte interface can be effectively reduced, and the reversible and stable electrochemical deposition stripping of calcium ions can be realized.
Comparative example 2
In the preparation process of the symmetrical battery and the secondary calcium ion battery in the comparative example 2 and the example 1, all the steps and materials used are the same except that the negative electrodes used for the symmetrical battery and the secondary calcium ion battery are all calcium metal, and the charge-discharge interval selection area of the secondary calcium ion battery is 0.4-2.2V. FIG. 8 is a graph showing the in-plane current density of 0.2mA cm for the calcium metal symmetrical cell of comparative example 2 -2 The dough kneading capacity density is 0.2mAh cm -2 The time voltage profile below. As can be seen from fig. 8, the calcium metal symmetrical battery of comparative example 2 has a maximum voltage hysteresis of about 0.34V in the first 5 cycles, but a sharp increase in voltage hysteresis (about 2.23V) after the 6 th cycle. It is clear from this that the voltage hysteresis of the symmetric battery using the calcium metal as the electrode changes very much during the cycle, which means that the deposition and stripping reaction of calcium ions on the calcium metal is extremely difficult and unstable.
The symmetrical cells of comparative example 1 and comparative example 2 had an in-plane current density of 0.2mA cm -2 Dough kneading capacity densityIs 0.2mAh cm -2 The stability under conditions is shown in Table 2.
Table 2 stability of symmetrical batteries of example 1 and comparative example 2
Table 2 shows the stability of the symmetrical cells of example 1 and comparative example 2. It can be seen from table 2 that under the aqueous-acetonitrile hybrid calcium ion electrolyte solutions 1 to 20, the active calcium metal and the aqueous-acetonitrile hybrid calcium ion electrolyte solution still undergo strong interactions, so that the problems of passivation and gas production of the calcium metal are very serious. Therefore, the charge transfer barrier at the calcium metal-electrolyte interface is very high, eventually leading to very poor electrochemical performance of the symmetric cell, which can only run for 7h. In contrast, the calcium-zinc alloy cathode formed in situ by electrochemistry can effectively relieve calcium metal passivation through alloying, inhibit dendrite growth and ensure overlength stable calcium stripping/electroplating. At 0.2mAcm -2 The dough kneading capacity density is 0.2mAh cm -2 Conventional cycle stability tests were performed with cycle times even exceeding 1600 hours.
FIG. 9 is a charge and discharge curve of the assembled secondary calcium ion battery of comparative example 2 at a current density of 0.1A/g. As can be seen from fig. 9, the secondary calcium ion battery assembled in comparative example 2 has a voltage plateau of up to about 1.93V at a current density of 0.1A/g, due to the low redox potential of the calcium metal. Fig. 10 is a graph of the rate performance of the assembled secondary calcium ion battery of comparative example 2. As can be seen from fig. 10, the capacity of the secondary calcium ion battery assembled in comparative example 2 was almost 0 after 6 cycles of the rate stability test, because the calcium metal negative electrode was rapidly passivated in the electrochemical reaction, resulting in failure of the calcium metal negative electrode, and finally limiting the cycle life of the secondary calcium ion battery manufactured in comparative example 2.
In summary, the metal foil which can be alloyed with calcium ions is directly used as the negative electrode current collector, and after the battery is assembled, the metal foil can form calcium alloy in situ, or the electrochemically prepared calcium alloy is directly used as the electrode, and the electrochemical stability of the two modes is superior to that of calcium metal.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The water-based organic hybridization secondary calcium ion battery based on electrochemical formation of the calcium alloy negative electrode comprises a battery negative electrode, electrolyte, a diaphragm and a battery positive electrode, and is characterized in that the battery negative electrode is the calcium alloy negative electrode; the electrolyte is a water system-organic hybridized calcium ion electrolyte; the active material of the battery anode is Prussian blue active material; the water system-organic hybridized calcium ion electrolyte is prepared by mixing and dissolving an organic solvent, calcium salt and deionized water, and fully stirring.
2. The aqueous-based organic hybrid secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode according to claim 1, wherein the calcium alloy negative electrode is obtained by polishing a metal foil to remove a surface oxide layer, then immersing the polished metal foil with dilute acid to remove a residual oxide layer, and finally cleaning the polished metal foil with deionized water and absolute ethyl alcohol to obtain the metal foil with the surface oxide layer removed; cutting the metal foil with the oxide layer removed, taking the metal foil cut piece as a positive electrode and a negative electrode of the symmetrical battery, taking a water system-organic hybridization calcium ion electrolyte as the electrolyte, assembling the battery into a CR2032 button battery, and disassembling the battery after charge-discharge circulation; or directly using a metal foil which is alloyed with calcium ions as a negative electrode current collector, and forming the calcium alloy in situ by the metal foil after the battery is assembled.
3. The aqueous-organic hybrid secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode according to claim 2, wherein the metal foil is zinc foil, tin foil, nickel foil, molybdenum foil, copper foil or manganese foil.
4. The aqueous-based organic hybrid secondary calcium ion battery for electrochemically forming a negative electrode of a calcium alloy according to claim 2, wherein the dilute acid is dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid, and the concentration of the dilute acid is 0.5-2 mol/L.
5. The aqueous organic hybrid secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode according to claim 1, wherein the organic solvent is one or more of nitrile organic solvents, ether organic solvents and ester organic solvents.
6. The aqueous-organic hybrid secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode according to claim 5, wherein the nitrile-based organic solvent is one or more of acetonitrile, succinonitrile or adiponitrile; the ether organic solvent is ethylene glycol dimethyl ether or/and triethylene glycol dimethyl ether; the ester organic solvent is at least one of propylene carbonate, ethylene carbonate or diethyl carbonate.
7. The aqueous organic hybrid secondary calcium ion battery based on electrochemical formation of a calcium alloy negative electrode according to claim 1, wherein the calcium salt is one or more of calcium triflate, calcium bis (trifluoromethylsulfonyl) imide, calcium bisfluorosulfonyl imide, calcium perchlorate, calcium tetrafluoroborate, calcium hexafluorophosphate, calcium nitrate, calcium fluoride, and calcium chloride.
8. The aqueous-based organic hybrid secondary calcium ion battery for electrochemically forming a negative electrode of a calcium alloy according to claim 1, wherein the prussian blue active material is nickel-manganese prussian blue, copper prussian blue or cobalt prussian blue.
9. The aqueous-organic hybrid secondary calcium ion battery based on electrochemical formation of a negative electrode of a calcium alloy according to claim 1, wherein the molar ratio of the organic solvent, the calcium salt and deionized water is 1 (10-30): 10-30.
10. Use of a secondary calcium ion battery according to any one of claims 1-9 in an energy storage device or consumer.
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