CN117766859A - High specific energy fast-charging organic sodium ion battery - Google Patents
High specific energy fast-charging organic sodium ion battery Download PDFInfo
- Publication number
- CN117766859A CN117766859A CN202311652728.8A CN202311652728A CN117766859A CN 117766859 A CN117766859 A CN 117766859A CN 202311652728 A CN202311652728 A CN 202311652728A CN 117766859 A CN117766859 A CN 117766859A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- sodium ion
- sodium
- ion battery
- high specific
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 claims abstract description 94
- 239000000243 solution Substances 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000002070 nanowire Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000006258 conductive agent Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 9
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- -1 sodium hexafluorophosphate Chemical group 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002109 single walled nanotube Substances 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000006757 chemical reactions by type Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 5
- 229910052935 jarosite Inorganic materials 0.000 description 48
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 244000061661 Orchis Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011474 orchiectomy Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of organic energy storage devices, and discloses a high-specific-energy fast-charging organic sodium ion battery. The high specific energy fast-charging organic sodium ion battery comprises an anode, a cathode and electrolyte; wherein the electrolyte is sodium ion organic electrolyte; mixing ferrous sulfate heptahydrate, a metal source, manganese acetate and sulfuric acid solution for reaction to obtain an electrode material; mixing an electrode material, a conductive agent and water, and drying to obtain a capacitive self-supporting electrode material, namely a positive electrode; mixing tetrabutyl titanate ethanol solution and sodium hydroxide aqueous solution for reaction and annealing to obtain a nano titanate wire; and mixing the titanate nanowire, the conductive agent and water, and drying to obtain the reactive self-supporting electrode material, namely the negative electrode. The positive electrode and the negative electrode of the high specific energy fast-charging organic sodium ion battery are self-supporting structures, inert binders and current collectors are not existed, the energy density is high, meanwhile, the excellent conductivity of the conductive agent endows the device with high power density, and the battery can realize fast charging.
Description
Technical Field
The invention relates to the technical field of organic energy storage devices, in particular to a high specific energy fast-charging organic sodium ion battery.
Background
With the rapid rise of electric automobiles, portable/wearable electronic devices and large-sized fixed energy storage devices, the demands of low-cost and high-safety energy storage systems with high energy density and high power density are urgent, so how to integrate the advantages of high energy density of batteries and high power density of super capacitors into a whole is important to design novel electrochemical energy storage devices to meet the energy storage demands of future multifunctional electronic devices. In addition, the sodium reserve in the crust is 420 times of the lithium reserve, so that the sodium ion energy storage device has lower cost and larger sustainable development potential in theory, and is expected to replace part of the markets of lithium ion batteries. However, there is a huge kinetic gap and capacity mismatch between the battery electrode and the capacitor electrode, so the power density and the cycle life of the energy storage device are limited by the battery electrode, and the energy density is limited by the capacitor electrode. These disadvantages greatly limit the electrochemical performance and utility of sodium ion batteries.
Therefore, how to reduce the reaction kinetics gap and the capacity gap between the capacitor electrode and the battery electrode is important.
Disclosure of Invention
The invention aims to provide a high specific energy fast-charge organic sodium ion battery, which solves the problems of huge dynamic gap and capacity mismatch between a battery electrode and a capacitor electrode in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high specific energy fast-charging organic sodium ion battery, which comprises an anode, a cathode and electrolyte, wherein the anode is connected with the electrolyte;
the positive electrode is a capacitive self-supporting electrode material;
the negative electrode is a reaction type self-supporting electrode material;
the electrolyte is sodium ion organic electrolyte;
the preparation method of the capacitive self-supporting electrode material comprises the following steps:
mixing ferrous sulfate heptahydrate, a metal source, manganese acetate and sulfuric acid solution, and performing a first reaction to obtain an electrode material;
mixing an electrode material, a conductive agent and water, and drying to obtain a capacitance type self-supporting electrode material;
the metal source is potassium nitrate, sodium chloride, sodium sulfate or lead nitrate;
the preparation method of the reactive self-supporting electrode material comprises the following steps:
mixing tetrabutyl titanate ethanol solution and sodium hydroxide aqueous solution, performing a hydrothermal reaction, and annealing the obtained product after the hydrothermal reaction is finished to obtain a titanate nanowire;
and mixing the titanate nanowire, the conductive agent and water, and drying to obtain the reactive self-supporting electrode material.
Preferably, in the above-mentioned high specific energy fast-charging organic sodium ion battery, the ratio of the ferrous sulfate heptahydrate, the metal source, the manganese acetate and the sulfuric acid solution is 1 to 3mol: 2-4 mol:0.1 to 0.3mol: 20-60L;
the concentration of the sulfuric acid solution is 0.01-0.1 mol/L.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the temperature of the first reaction is 80 to 100 ℃, and the time of the first reaction is 2 to 4 hours.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the mass ratio of the electrode material to the conductive agent is 0.1:1 to 10.
Preferably, in the high specific energy fast-charge organic sodium ion battery, the concentration of the tetrabutyl titanate ethanol solution is 0.1-0.5 mol/L;
the concentration of the sodium hydroxide aqueous solution is 8-15 mol/L;
the volume ratio of the tetrabutyl titanate ethanol solution to the sodium hydroxide aqueous solution is 1-3: 1 to 3.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the temperature of the hydrothermal reaction is 180-250 ℃, and the time of the hydrothermal reaction is 10-15 hours;
the annealing conditions are as follows: the atmosphere is a mixed gas of argon and hydrogen, the heating rate is 1-3 ℃/min, the temperature is 400-500 ℃, and the annealing time is 1.5-3 h.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the mass ratio of the titanate nanowires to the conductive agent is 0.1:1 to 10.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the ratio of the conductive agent to water is independently 1 to 10g:0.1 to 0.3L;
the conductive agent is independently single-wall carbon nanotube slurry, two-dimensional transition metal carbide slurry or two-dimensional graphene sheet slurry.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the mass ratio of the positive electrode to the negative electrode is 1.5: 1-2: 1, a step of;
the sodium ion organic electrolyte is an ether solution of sodium salt;
the concentration of the ether solution of the sodium salt is 0.5-1.5 mol/L.
Preferably, in the above-mentioned high specific energy fast-charge organic sodium ion battery, the sodium salt in the sodium ion electrolyte is sodium hexafluorophosphate, sodium perchlorate or sodium trifluorosulfonimide;
the ether solution in the sodium ion organic electrolyte is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.
Compared with the prior art, the invention has the following beneficial effects:
(1) The self-supporting electrode without the substrate does not contain inert binder particles and a current collector, has high energy density and continuous electronic conductive paths, and the active material is tightly packed in a three-dimensional conductive network, so that the device has high power density and the electronic conductivity of the material is improved; in addition, the gaps in the self-supporting electrode can enable electrolyte to fully infiltrate electrode materials, so that an ion diffusion path is effectively shortened. Therefore, the self-supporting electrode without substrate and binder has better reaction kinetics and energy density as a mixed conductor of electronic conduction and ionic conduction.
(2) In the ether electrolyte with high ionic conductivity, the ether electrolyte is matched with intercalation pseudo-capacitance type materials with high specific capacity, and the energy density of the whole device is improved while the high power density is ensured by good matching of charges/quality under different current densities, so that the construction of an organic sodium ion battery with both high power density and high energy density is realized.
(3) The invention improves the reaction dynamics difference between the battery type electrode and the capacitor type electrode through reasonable electrode structure design, and assembles with the intercalation type pseudo-capacitor electrode material with high specific capacity, and builds the high specific energy sodium ion battery capable of being charged rapidly through accurate capacity matching.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a cyclic voltammogram of a capacitive self-supporting jarosite electrode material of example 1;
FIG. 2 is a linear relationship between the logarithm of peak current values and the logarithm of scan rate of the capacitive self-supporting jarosite electrode material of example 1;
FIG. 3 is a graph showing the capacitance contribution of the capacitive self-supporting jarosite electrode material of example 1;
FIG. 4 is a graph comparing the rate capability of the slurry coated jarosite electrode material with the capacitive self-supporting jarosite electrode material of example 1;
FIG. 5 is a charge-discharge curve of the capacitive self-supporting jarosite electrode material of example 1;
FIG. 6 is a constant current charge-discharge curve of the reactive self-supporting sodium titanate nanowire electrode material of example 2;
FIG. 7 is a graph showing the rate performance of the reactive self-supporting sodium titanate nanowire electrode material of example 2;
FIG. 8 is a graph showing the cycling performance of the reactive self-supporting sodium titanate nanowire electrode material of example 2 at different current densities;
FIG. 9 is a cyclic voltammogram of a capacitive self-supporting jarosite electrode material versus a reactive self-supporting sodium titanate nanowire electrode material at a positive to negative mass ratio of 1.5 in example 3;
FIG. 10 is the charge stored in the capacitive self-supporting jarosite electrode material and the reactive self-supporting sodium titanate nanowire electrode material at a positive to negative mass ratio of 1.5 in example 3;
FIG. 11 is a charge and discharge plot of a jarosite// sodium titanate high specific energy fast-charge organic sodium ion battery of example 4;
FIG. 12 is a plot of the rate performance of the jarosite// sodium titanate high specific energy fast-charge organic sodium ion battery of example 4;
FIG. 13 is a graph of the cycling performance of the jarosite// sodium titanate high specific energy fast-charge organic sodium ion battery of example 4;
FIG. 14 is an energy density-power density plot for a jarosite// sodium titanate high specific energy fast-charged organic sodium ion battery of example 4.
Detailed Description
The invention provides a high specific energy fast-charging organic sodium ion battery, which comprises an anode, a cathode and electrolyte, wherein the anode is connected with the electrolyte;
the positive electrode is a capacitive self-supporting electrode material;
the negative electrode is a reaction type self-supporting electrode material;
the electrolyte is sodium ion electrolyte.
In the invention, the preparation method of the capacitive self-supporting electrode material comprises the following steps:
mixing ferrous sulfate heptahydrate, a metal source, manganese acetate and sulfuric acid solution, and performing a first reaction to obtain an electrode material;
and mixing the electrode material, the conductive agent and water, and drying to obtain the capacitive self-supporting electrode material.
In the present invention, the ratio of the ferrous sulfate heptahydrate, the metal source, the manganese acetate and the sulfuric acid solution is preferably 1 to 3mol: 2-4 mol:0.1 to 0.3mol:20 to 60L, more preferably 1.5 to 2.8mol:2.2 to 3.6mol:0.12 to 0.25mol:30 to 55L, more preferably 1.8 to 2.5mol:3 to 3.5mol:0.15 to 0.18mol: 35-40L.
In the present invention, the metal source is preferably potassium nitrate, sodium chloride, sodium sulfate or lead nitrate, more preferably potassium nitrate, sodium chloride or sodium sulfate, and still more preferably potassium nitrate.
In the present invention, the concentration of the sulfuric acid solution is preferably 0.01 to 0.1mol/L, more preferably 0.3 to 0.8mol/L, and still more preferably 0.5 to 0.6mol/L.
In the present invention, the temperature of the first reaction is preferably 80 to 100 ℃, more preferably 85 to 95 ℃, still more preferably 86 to 90 ℃; the time of the first reaction is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and still more preferably 2.75 to 3 hours.
In the present invention, the heating means for the first reaction is preferably water bath heating.
In the present invention, after the first reaction is completed, the method further comprises: after the obtained product is naturally cooled, washing is carried out by using water and absolute ethyl alcohol in sequence, and then drying is carried out at 80 ℃.
In the present invention, the mass ratio of the electrode material to the conductive agent is preferably 0.1:1 to 10, more preferably 0.1:3 to 8, more preferably 0.1:5 to 6.25.
In the invention, the specific process of mixing the electrode material, the conductive agent and the water is as follows: firstly, mixing the electrode material with water, performing ultrasonic dispersion for 10min, then adding the conductive agent, and performing ultrasonic dispersion for 40min.
In the present invention, after the electrode material, the conductive agent and the water are mixed, the method further comprises: forming a film; the film forming method comprises spraying, knife coating, vacuum suction filtration or reduced pressure suction filtration.
In the invention, the post-treatment process of the capacitive self-supporting electrode material comprises the following steps: and tabletting and drying the capacitive self-supporting electrode material.
In the invention, the preparation method of the reactive self-supporting electrode material comprises the following steps:
mixing tetrabutyl titanate ethanol solution and sodium hydroxide aqueous solution, performing a hydrothermal reaction, and annealing the obtained product after the hydrothermal reaction is finished to obtain a titanate nanowire;
and mixing the titanate nanowire, the conductive agent and water, and drying to obtain the reactive self-supporting electrode material.
In the present invention, the concentration of the tetrabutyl titanate ethanol solution is preferably 0.1 to 0.5mol/L, more preferably 0.15 to 0.3mol/L, and still more preferably 0.2 to 0.25mol/L.
In the present invention, the concentration of the aqueous sodium hydroxide solution is preferably 8 to 15mol/L, more preferably 9 to 13mol/L, and still more preferably 10 to 12mol/L.
In the invention, the volume ratio of the tetrabutyl titanate ethanol solution to the sodium hydroxide aqueous solution is preferably 1-3: 1 to 3, more preferably 1.2 to 2.5:1.2 to 2.5, more preferably 1.5 to 2:1.5 to 2.
In the invention, the specific process of mixing the tetrabutyl titanate solution and the sodium hydroxide aqueous solution comprises the following steps: the tetrabutyl titanate solution was dropped into the aqueous sodium hydroxide solution, followed by stirring for 30 minutes.
In the present invention, the temperature of the hydrothermal reaction is preferably 180 to 250 ℃, more preferably 190 to 240 ℃, still more preferably 200 to 220 ℃; the time of the hydrothermal reaction is preferably 10 to 15 hours, more preferably 11 to 14 hours, and still more preferably 12 to 13 hours.
In the present invention, after the hydrothermal reaction is completed, the method further comprises: the obtained product is washed to be neutral by water and absolute ethyl alcohol in sequence, and then is dried.
In the present invention, the annealing conditions are as follows: the atmosphere is preferably a mixture of argon and hydrogen, and the rate of temperature rise is preferably 1 to 3 ℃/min, more preferably 1.2 to 2.5 ℃/min, and even more preferably 1.5 to 2 ℃/min; the temperature is preferably 400 to 500 ℃, more preferably 420 to 480 ℃, and even more preferably 450 ℃; the annealing time is preferably 1.5 to 3 hours, more preferably 1.75 to 2.5 hours, and still more preferably 2 hours. The method comprises the steps of carrying out a first treatment on the surface of the
The volume ratio of the argon to the hydrogen is preferably 90-97: 3 to 10, more preferably 92 to 96:4 to 8, more preferably 95:5.
in the present invention, the mass ratio of the titanate nanowire to the conductive agent is preferably 0.1:1 to 10, more preferably 0.1:3 to 8, more preferably 0.1:5 to 6.25.
In the invention, the specific process of mixing the titanate nanowire, the conductive agent and the water comprises the following steps: mixing sodium titanate nanowires with water, performing ultrasonic dispersion for 10min, adding a conductive agent, and performing ultrasonic dispersion for 40min.
In the present invention, after the nano-wires of titanate, the conductive agent and water are mixed, the method further comprises: forming a film; the film forming method comprises spraying, knife coating, vacuum suction filtration or reduced pressure suction filtration.
In the invention, the post-treatment process of the reactive self-supporting electrode material is as follows: and tabletting and drying the capacitive self-supporting electrode material.
In the present invention, the ratio of the conductive agent to water is preferably 1 to 10g:0.1 to 0.3L, more preferably 1 to 8g:0.1 to 0.25L, more preferably 2 to 6g: 0.15-0.2L.
In the present invention, the conductive agent is independently preferably a single-walled carbon nanotube paste, a two-dimensional transition metal carbide paste or a two-dimensional graphene sheet paste, more preferably a single-walled carbon nanotube paste or a two-dimensional transition metal carbide paste, and still more preferably a single-walled carbon nanotube paste.
In the present invention, the single-walled carbon nanotube slurry is preferably commercially available from Orchis hong Kong Inc. under the trademark TUBALL TM BATT H 2 O 0.4％。
In the present invention, the mass ratio of the positive electrode to the negative electrode is preferably 1.5: 1-2: 1, further preferably 1.5:1 to 1.8:1, more preferably 1.5:1 to 1.6:1.
in the present invention, the sodium ion organic electrolytic solution is preferably an ether solution of sodium salt.
In the present invention, the concentration of the ether solution of the sodium salt is preferably 0.5 to 1.5mol/L, more preferably 0.6 to 1.2mol/L, and still more preferably 0.8 to 1mol/L.
In the present invention, the sodium salt in the sodium ion organic electrolyte is preferably sodium hexafluorophosphate, sodium perchlorate or sodium trifluorosulfimide, more preferably sodium hexafluorophosphate or sodium perchlorate, and still more preferably sodium hexafluorophosphate.
In the present invention, the ether solution in the sodium ion organic electrolyte is preferably one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether, more preferably one or two of ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and even more preferably ethylene glycol dimethyl ether.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The single-walled carbon nanotube slurries described in examples 1 and 2 below are all available from Orchis hong Kong Inc. under the trademark TUBALL TM BATT H 2 O0.4% of product.
Example 1
A preparation method of a capacitive self-supporting jarosite electrode material comprises the following steps:
(1) Sequentially dissolving 5.02g of ferrous sulfate heptahydrate, 3.06g of potassium nitrate and 0.28g of manganese acetate in 400mL of 0.01mol/L sulfuric acid solution, then placing in a water bath at 90 ℃ for stirring reaction for 3 hours, naturally cooling after the reaction is finished, sequentially cleaning with deionized water and absolute ethyl alcohol, and then placing in a blast drying oven at 80 ℃ for drying to obtain jarosite electrode material;
(2) Adding 10mg of jarosite electrode material into 15mL of deionized water, performing ultrasonic dispersion for 10min, adding 0.625g of single-wall carbon nanotube slurry, performing ultrasonic dispersion for 40min to obtain suspension, performing vacuum filtration to form a black film on a filter membrane, drying in a shade place in a room, removing the black film from the filter membrane to obtain a capacitive self-supporting jarosite electrode material, pressing the capacitive self-supporting jarosite electrode material into a wafer with the diameter of 12mm by using a tablet press, and then drying in a vacuum drying oven at 80 ℃ for 12h.
The capacitive self-supporting jarosite electrode material is used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, 1mol/L diethylene glycol dimethyl ether solution of sodium hexafluorophosphate is used as an electrolyte, and the electrolyte is put into a glove box (H) filled with argon 2 O<0.01ppm，O 2 <0.01 ppm) was assembled into a CR2023 type coin cell for cyclic voltammetry and constant current charge-discharge testing.
Cyclic voltammograms of the capacitive self-supporting jarosite electrode material at different scan rates are shown in figure 1. As can be seen from fig. 1, the cyclic voltammogram has a pair of very broad redox peaks, both at smaller and larger scan rates, which illustrates that the sodium storage mechanism of the capacitive self-supporting jarosite electrode material is a pseudocapacitive mechanism.
Further combining a power law formula to perform qualitative analysis on a sodium storage mechanism of the capacitive self-supporting jarosite electrode material, and fitting linear relations obtained by the logarithm of peak current values and the logarithm of scanning rates at different scanning rates are shown in figure 2. As can be seen from fig. 2, the slope values of the linear relationship obtained by fitting the logarithm of the peak current value and the logarithm of the scanning rate are 0.8738 and 0.9065, respectively, which are both greater than 0.5, under different scanning rates, which indicates that the sodium storage process of the capacitive self-supporting jarosite electrode material is dominant in surface capacitance control and is less in solid diffusion control.
The capacitance contribution graph of the capacitive self-supporting jarosite electrode material during sodium storage at different scan rates is shown in fig. 3. As can be seen from FIG. 3, the surface capacitance control contributes to the capacitance at scan rates of 0.2, 0.4, 0.6, 0.8, 1.0mV/s94.08%, 95.50%, 97.35%, 98.56% and 99.13%, respectively. This is a full indication that the charge storage of jarosite is largely dependent on pseudocapacitive contribution, na inside the electrode + Can diffuse rapidly and perform fast Faraday reaction, and has excellent reaction kinetics while providing more capacity.
The ratio performance comparison of the slurry coated jarosite electrode material and the capacitive self-supporting jarosite electrode material is shown in fig. 4. The preparation method of the jarosite electrode material coated with the slurry comprises the following steps:
KFE with mass ratio of 7:2:1 3 (SO 4 ) 2 (OH) 6 Adding an active material, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder into N-methyl pyrrolidone (NMP) to obtain a mixed solution; the PVDF content in the mixed solution is 5wt%; adding 5 zirconia balls into the mixed solution, and ball milling for 3 times by adopting a slurry homogenizing machine for 3min each time to obtain slurry; uniformly coating the obtained slurry on an aluminum foil current collector by adopting a four-side preparation device (200 mu m), transferring to a vacuum drying oven at 120 ℃ for drying for 12 hours, and cutting into electrode plates with the diameter of 12mm by using a sheet-forming machine after the drying is finished, thus obtaining the jarosite electrode material coated with the slurry.
As can be seen from fig. 4, the capacitive self-supporting jarosite electrode material can provide specific capacities of 123, 115, 110, 100, 84, 73, 61mAh/g at current densities of C/5, C/2, 1C, 2C, 5C, 10C, 20C (1c=160.5 mAh/g), and has a specific capacity of 53mAh/g (43% at about 0.5C) even at current densities as high as 30C, showing excellent rate performance; whereas the slurry coated jarosite electrode material provided a much lower capacity (45, 34, 24, 13mAh/g at C/5, C/2, 1C, 2C current densities, respectively) than the capacitive self-supporting jarosite electrode material, even at a current density of 5C the capacity was already close to 0, and rapid charging and discharging was not possible. The capacitor type self-supporting jarosite electrode material mainly benefits from the fact that the capacitor type self-supporting jarosite electrode material does not contain an insulating binder, and the three-dimensional conductive network brings higher electronic conductivity to the electrode, so that the capacitor type self-supporting jarosite electrode material has better rate capability; in addition, the gap between the network structures in the capacitive self-supporting jarosite electrode material increases the contact area between the electrode and the electrolyte, so that the active material is more exposed to the electrolyte, the reactive sites are increased, and the electrode capacity is also obviously improved.
The charge-discharge curves of the capacitive self-supporting jarosite electrode material at different rates are shown in fig. 5. As can be seen from fig. 5, the charge-discharge curves at both small and large currents have no obvious plateau and are nearly linear, which corresponds to the cyclic voltammetry test results, and all prove that the capacitive self-supporting jarosite electrode material is an intercalation pseudo-capacitance mechanism during sodium storage. Therefore, it has a higher specific capacity while maintaining excellent rate performance.
Example 2
The preparation method of the reactive self-supporting sodium titanate nanowire electrode material comprises the following steps:
(1) Dripping 20mL of 0.2mol/L tetrabutyl titanate ethanol solution into 20mL of 10mol/L sodium hydroxide aqueous solution, stirring for 30min after dripping, transferring into a polytetrafluoroethylene liner, performing hydrothermal reaction at 200 ℃ for 12h, cleaning the obtained product to be neutral by adopting deionized water and absolute ethyl alcohol in sequence after the reaction is finished, and drying in a blast drying box; subsequently in Ar/H 2 (V Ar ：V H2 =95: 5) Annealing is carried out in the mixed atmosphere, the heating rate of the annealing is 2 ℃/min, the annealing temperature is 450 ℃, and the annealing time is 2h, so as to obtain the nano-wire of the titanate;
(2) Adding 10mg of sodium titanate nanowire into 15mL of deionized water, performing ultrasonic dispersion for 10min, adding 0.625g of single-walled carbon nanotube slurry, performing ultrasonic dispersion for 40min to obtain suspension, performing vacuum suction filtration to form a black film on a filter membrane, drying at a shade place in a room, and then removing the black film from the filter membrane to obtain a reactive self-supporting sodium titanate nanowire electrode material, then punching the reactive self-supporting sodium titanate nanowire material into a wafer with the diameter of 12mm by using a tablet press, and then drying in a vacuum drying oven at 80 ℃ for 12h.
The reaction type self-supporting sodium titanate nanowire electrode material is used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1mol/L hexafluoro is used as a reference electrodeSodium phosphate in diethylene glycol dimethyl ether as an electrolyte, a glove box (H 2 O<0.01ppm，O 2 <0.01 ppm) was assembled into a CR2023 type coin cell battery for constant current charge and discharge testing.
The constant current charge-discharge curves of the reactive self-supporting sodium titanate nanowire electrode materials at different multiplying powers are shown in fig. 6. As can be seen from FIG. 6, the voltage at-0.3V and-0.5V (vs.Na + A pair of distinct platforms exist at/Na) and provide a capacity exceeding 50% of the total capacity.
The rate performance graph of the reactive self-supporting sodium titanate nanowire electrode material is shown in fig. 7. As can be seen from fig. 7, at current densities of C/5, C/2, 1C, 2C, 5C, 10C, 20C (1c=177 mAh/g), the reactive self-supporting sodium titanate nanowire electrode material had specific capacities of about 191, 188, 170, 153, 130, 112, 91mAh/g, respectively, and the specific capacity of 85mAh/g (44.5% at about 0.5C) was maintained even at an ultra-large current density of 30C (5.3A/g), and when the current density was returned to the small current density of C/5 again, the capacity was restored to 185mAh/g, indicating that the reactive self-supporting sodium titanate nanowire electrode material had excellent rate performance and cycle stability.
The cycling performance graph of the reactive self-supporting sodium titanate nanowire electrode material at different current densities is shown in fig. 8. As can be seen from fig. 8, the capacity retention rates after 1000 cycles at current densities of 1C, 2C, and 5C were 78.19%, 82.25%, and 89.95%, respectively, showing excellent cycle life.
The electrochemical test results show that the reactive self-supporting sodium titanate nanowire electrode material has low working potential (-0.3V vs. Na) + Na), high specific capacity (191 mAh/g), excellent rate performance and cycling stability, the battery-type electrode used as a battery will be expected to match with the capacitor-type electrode with rapid reaction kinetics, while maintaining higher power density while improving the energy density of the device.
Example 3
The capacitive self-supporting jarosite electrode material is used as a working electrode, a metal sodium sheet is used as a counter electrode and a reference electrode, and 1mol/L sodium hexafluorophosphate diethylene glycol dimethyl ether solution is used as an electrolyteIn a glove box filled with argon (H 2 O<0.01ppm，O 2 <0.01 ppm) of a CR2023 type button cell; the method comprises the steps of taking a reactive self-supporting sodium titanate nanowire electrode material as a working electrode, taking a metal sodium sheet as a counter electrode and a reference electrode, taking 1mol/L diethylene glycol dimethyl ether solution of sodium hexafluorophosphate as an electrolyte, and putting the electrolyte in a glove box (H) filled with argon 2 O<0.01ppm，O 2 <0.01 ppm) of a CR2023 type coin cell was assembled.
To optimize the performance of the battery, the stored charge values of the positive and negative electrodes at each current are compared. The mass ratio of the negative electrode to the positive electrode (the reactive self-supporting sodium titanate nanowire electrode material to the capacitive self-supporting jarosite electrode material) is 1:1.5 the cyclic voltammogram of the capacitive self-supporting jarosite electrode material and the reactive self-supporting sodium titanate nanowire electrode material at a scan rate of 1.0mV/s is shown in fig. 9, and the capacity ratio of the positive electrode to the negative electrode is calculated by integration to be close to 1, which shows that the two materials have good suitability.
The mass ratio of the cathode to the anode is 1: the capacity of the positive and negative electrodes stored at 1.5 f at different currents is shown in fig. 10. As can be seen from fig. 10, at the current of 0.032mA, 1.593mA and 4.779mA, the positive electrode can provide the capacity of 0.190, 0.110 and 0.080mAh, the negative electrode can provide the capacity of 0.178, 0.116 and 0.076mAh, and the result shows that the capacities of the positive electrode and the negative electrode can be well matched under the condition of smaller or larger current, which provides guarantee for the electrochemical performance of the assembled high specific energy fast-charge organic sodium ion battery.
Example 4
Jarosite// sodium titanate high specific energy fast-charge organic sodium ion battery:
taking the capacitive self-supporting jarosite electrode material prepared in the example 1 as a positive electrode, and the reactive self-supporting sodium titanate nanowire electrode material prepared in the example 2 as a negative electrode, wherein 1mol/L of diethylene glycol dimethyl ether solution of sodium hexafluorophosphate is used as an electrolyte; wherein the mass ratio of N/P is 1:1.5.
the charge and discharge curves of jarosite// sodium titanate high specific energy fast-charge organic sodium ion batteries are shown in figure 11. As can be seen from fig. 11, the charge-discharge curves at each current density have no plateau, are almost linear, and are typical battery characteristics.
The rate performance graph of jarosite// sodium titanate high specific energy fast-charged organic sodium ion batteries is shown in fig. 12. As can be seen from fig. 12, the specific capacities of 165.6, 155.3, 145.0, 135.0, 122.9, 109.8, 90.7, 83.1mAh/g (based on the negative electrode) and 5.31A/g (30C) were found to be respectively found to have specific capacities of 165.6, 155.3, 145.0, 135.0, 122.9, 109.8, 90.7, 83.1mAh/g in the voltage range of 0.5 to 4.0V, respectively, and the capacity retention rate was found to be 50.2% in the case of 5.31A/g (30C), indicating that the battery has excellent rate performance, and the capacity was increased to 166.3mAh/g again when the battery was returned to the small current density of 0.035A/g again, thereby proving the device has excellent stability.
The cycling performance of the jarosite// sodium titanate high specific energy fast-charged organic-based sodium-ion cell at current densities of 5C (0.885A/g) and 10C (1.77A/g) is shown in FIG. 13. As can be seen from fig. 13, the capacity retention rates after 500 cycles were 81.4% and 85.9%, respectively, and showed superior cycle stability than other jarosite-based positive electrode-related studies.
The energy density and power density of the jarosite// sodium titanate high specific energy fast-charge organic sodium ion battery were calculated from the charge-discharge curves at different current densities, and the energy density-power density diagram of the device is shown in fig. 14. As can be seen from FIG. 14, the sodium ion battery jarosite// sodium titanate sodium ion battery can provide up to 123.3 Wh.kg -1 Energy density of (C) and 3625.9 W.kg -1 These values are superior to some of the organic sodium ion batteries based on titanium-based cathodes reported previously.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The high specific energy fast-charging organic sodium ion battery is characterized by comprising a positive electrode, a negative electrode and electrolyte;
the positive electrode is a capacitive self-supporting electrode material;
the negative electrode is a reaction type self-supporting electrode material;
the electrolyte is sodium ion organic electrolyte;
the preparation method of the capacitive self-supporting electrode material comprises the following steps:
mixing ferrous sulfate heptahydrate, a metal source, manganese acetate and sulfuric acid solution, and performing a first reaction to obtain an electrode material;
mixing an electrode material, a conductive agent and water, and drying to obtain a capacitance type self-supporting electrode material;
the metal source is potassium nitrate, sodium chloride, sodium sulfate or lead nitrate;
the preparation method of the reactive self-supporting electrode material comprises the following steps:
mixing tetrabutyl titanate ethanol solution and sodium hydroxide aqueous solution, performing a hydrothermal reaction, and annealing the obtained product after the hydrothermal reaction is finished to obtain a titanate nanowire;
and mixing the titanate nanowire, the conductive agent and water, and drying to obtain the reactive self-supporting electrode material.
2. The high specific energy fast charge organic sodium ion battery according to claim 1, wherein the ratio of ferrous sulfate heptahydrate, metal source, manganese acetate and sulfuric acid solution is 1-3 mol: 2-4 mol:0.1 to 0.3mol: 20-60L;
the concentration of the sulfuric acid solution is 0.01-0.1 mol/L.
3. The high specific energy fast charge organic sodium ion battery according to claim 1 or 2, wherein the temperature of the first reaction is 80-100 ℃, and the time of the first reaction is 2-4 hours.
4. The high specific energy fast charge organic sodium ion battery according to claim 3, wherein the mass ratio of the electrode material to the conductive agent is 0.1:1 to 10.
5. The high specific energy fast charge organic sodium ion battery according to claim 4, wherein the concentration of the tetrabutyl titanate ethanol solution is 0.1-0.5 mol/L;
the concentration of the sodium hydroxide aqueous solution is 8-15 mol/L;
the volume ratio of the tetrabutyl titanate ethanol solution to the sodium hydroxide aqueous solution is 1-3: 1 to 3.
6. The high specific energy fast charge organic sodium ion battery according to claim 4 or 5, wherein the temperature of the hydrothermal reaction is 180-250 ℃, and the time of the hydrothermal reaction is 10-15 hours;
the annealing conditions are as follows: the atmosphere is a mixed gas of argon and hydrogen, the heating rate is 1-3 ℃/min, the temperature is 400-500 ℃, and the annealing time is 1.5-3 h.
7. The high specific energy fast charge organic sodium ion battery according to claim 6, wherein the mass ratio of the titanate nanowires to the conductive agent is 0.1:1 to 10.
8. The high specific energy fast charge organic sodium ion battery according to claim 7, wherein the ratio of the conductive agent to water is independently 1 to 10g:0.1 to 0.3L;
the conductive agent is independently single-wall carbon nanotube slurry, two-dimensional transition metal carbide slurry or two-dimensional graphene sheet slurry.
9. The high specific energy fast charge organic sodium ion battery according to claim 7 or 8, wherein the mass ratio of positive to negative electrode is 1.5: 1-2: 1, a step of;
the sodium ion organic electrolyte is an ether solution of sodium salt;
the concentration of the ether solution of the sodium salt is 0.5-1.5 mol/L.
10. The high specific energy fast charge organic sodium ion battery according to claim 9, wherein the sodium salt in the sodium ion electrolyte is sodium hexafluorophosphate, sodium perchlorate or sodium trifluorosulfonimide;
the ether solution in the sodium ion organic electrolyte is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311652728.8A CN117766859A (en) | 2023-12-05 | 2023-12-05 | High specific energy fast-charging organic sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311652728.8A CN117766859A (en) | 2023-12-05 | 2023-12-05 | High specific energy fast-charging organic sodium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117766859A true CN117766859A (en) | 2024-03-26 |
Family
ID=90309641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311652728.8A Pending CN117766859A (en) | 2023-12-05 | 2023-12-05 | High specific energy fast-charging organic sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117766859A (en) |
-
2023
- 2023-12-05 CN CN202311652728.8A patent/CN117766859A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107369825B (en) | Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof | |
| CN109888245B (en) | Titanium niobium oxygen/carbon composite material with oxygen vacancy and carbon coating adjustment and preparation method and application thereof | |
| CN106058222B (en) | Polymer carbonization in-situ coated ferric trifluoride composite cathode material and preparation method thereof | |
| CN111384381A (en) | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof | |
| CN112864365A (en) | Nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and preparation method thereof | |
| WO2018209912A1 (en) | Tin sulfide/sulfur/few-layer graphene composite material, preparation method therefor and application thereof | |
| CN115566170B (en) | Preparation method of high-energy-density quick-charging lithium ion battery anode material | |
| CN109860958B (en) | Lithium-carbon dioxide battery and preparation method thereof | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| JP7413482B2 (en) | Manufacturing method for lithium ion battery negative electrode material | |
| CN113964320A (en) | Lithium ion battery and preparation method thereof | |
| Sui et al. | Highly dispersive CoSe 2 nanoparticles encapsulated in carbon nanotube-grafted multichannel carbon fibers as advanced anodes for sodium-ion half/full batteries | |
| CN115207304A (en) | Graphite cathode composite material, preparation method thereof and lithium ion battery | |
| CN114937809A (en) | Organic electrolyte with low freezing point and sodium ion battery using same | |
| CN115974114B (en) | Quick-charging graphite composite material and preparation method thereof | |
| CN116435467A (en) | Self-supporting positive electrode and preparation method and application thereof | |
| CN111063549A (en) | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor | |
| CN117766859A (en) | High specific energy fast-charging organic sodium ion battery | |
| CN113526486A (en) | Ultrahigh-sulfur-content hard carbon material and preparation method and application thereof | |
| CN115548311B (en) | Fluorine doped TiO2(B) rGO composite material and preparation method and application thereof | |
| CN111261857B (en) | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery | |
| CN112700967B (en) | Cu with high specific capacity2-xNegative electrode material of Se super capacitor | |
| CN114975994B (en) | Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof | |
| WO2022205151A1 (en) | Negative electrode active material, electrochemical apparatus, and electronic apparatus | |
| CN117352851A (en) | Electrolyte of low-temperature high-pressure sodium ion battery and sodium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |