CN113658808B - Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor - Google Patents
Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor Download PDFInfo
- Publication number
- CN113658808B CN113658808B CN202110824273.8A CN202110824273A CN113658808B CN 113658808 B CN113658808 B CN 113658808B CN 202110824273 A CN202110824273 A CN 202110824273A CN 113658808 B CN113658808 B CN 113658808B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- perovskite structure
- electrode material
- entropy ceramic
- preparation
- 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.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 2
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 239000002243 precursor Substances 0.000 description 35
- 229910010293 ceramic material Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the technical field of electrode material preparation, and provides a magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of a super capacitor X ) 1/5+ X O 3‑σ Wherein: x =0.3,0.4,0.5,0.6,0.7,0.8; the supercapacitor electrode material of the magnesium-doped perovskite structure high-entropy ceramic is successfully synthesized by controlling the process parameters such as element types, element proportion, preparation method, doping content, reaction time and temperature, and the like, and has the excellent characteristics of high capacity, good rate performance, cycle performance and the like. The preparation method is simple to operate, strong in controllability and wide in prospect.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of a supercapacitor.
Background
Energy problems are a difficult problem which troubles human beings for a long time in the process of industrial development, and the development of novel energy storage materials for application in energy conversion and energy storage is an important means for solving the energy problems. The super capacitor is used as a novel energy storage and conversion device and is between a traditional capacitor and a rechargeable battery, the super capacitor inherits the rapid charge-discharge characteristic of the traditional capacitor, and simultaneously has the excellent energy storage characteristic of the rechargeable battery, so that the super capacitor is an electrochemical energy storage device with excellent electrochemical characteristic and environmental friendliness, and attracts the extensive research of numerous scientific researchers.
The electrode materials adopted by the super capacitor mainly comprise metal oxides, conductive polymers, carbon materials and the like. The transition metal oxide in the metal oxide can have oxidation-reduction reaction to make the energy density of the transition metal oxide higher than that of the carbon material, and the perovskite structure high-entropy ceramic is prepared from the transition metal oxide, has a structure which is not available in other common metal oxides, and has the characteristics of various oxides inherited in performance, so that the perovskite structure metal oxide has distinctive performance characteristics. Perovskite-structured oxides may also possess different properties in the same elemental composition because ions of alkaline earth elements and transition metal elements of similar radii may be incompletely replaced and still maintain their original crystal structure after replacement, and perovskite-structured high-entropy oxides are widely used in high-performance batteries, special sensors, high-temperature resistant materials, variable resistivity, and inexpensive catalysts due to the variability of this characteristic. The A site cation and the B site cation are completely or partially replaced by special metal ions, and novel high-entropy ceramic materials with different structures and properties can be manufactured.
Disclosure of Invention
The invention provides a magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparing a super capacitor, wherein the magnesium-doped perovskite structure high-entropy ceramic electrode material is successfully synthesized by controlling the process parameters such as element types, element proportion, a preparation method, doping content, reaction time, temperature and the like, and has the excellent characteristics of high capacity, good rate capability, cycle performance and the like. The preparation method is simple to operate, strong in controllability and wide in prospect.
The invention adopts the following technical scheme: a magnesium-doped perovskite structure high-entropy ceramic electrode material is Ba (CoCrFeMnNiMg) X ) 1/5+X O 3-σ Wherein: x =0.3,0.4,0.5,0.6,0.7,0.8; σ is an oxygen vacancy.
The method for preparing the magnesium-doped perovskite structure high-entropy ceramic electrode material is synthesized by adopting a coprecipitation method, and comprises the following specific steps:
(1) Barium nitrate Ba (NO) 3 ) 2 Cobalt nitrate hexahydrate Co (NO) 3 ) 3 ·6H 2 0. Chromium nitrate nonahydrate Cr (NO) 3 ) 3 ·9H 2 0. Ferric nitrate nonahydrate Fe (NO) 3 ) 3 ·9H 2 0. Manganese nitrate tetrahydrate Mn (NO) 3 ) 2 ·4H 2 0. Nickel nitrate hexahydrate Ni (NO) 3 ) 2 ·6H 2 0. Magnesium chloride hexahydrate MgCl 2 ·6H 2 0 is dissolved in deionized water and is uniformly mixed to obtain a clear solution A; wherein: ba (NO) 3 ) 2 、Co(NO 3 ) 3 ·6H 2 0、Cr(NO 3 ) 3 ·9H 2 0、Fe(NO 3 ) 3 ·9H 2 0、Mn(NO 3 ) 2 ·4H 2 0、Ni(NO 3 ) 2 ·6H 2 0、MgCl 2 ·6H 2 The molar ratio of 0 is 5+ X:1:1:1:1:1: x, wherein: x =0.3,0.4,0.5,0.6,0.7,0.8;
(2) Adding 0.06mol of sodium carbonate into 200ml of aqueous alkali with the total concentration of 0.3mol/L, and uniformly stirring to obtain a clear solution B;
(3) Respectively placing the solution A and the solution B on a magnetic stirrer and stirring for 2 hours;
(4) Adding the solution B obtained in the step (3) into the solution A while stirring, and standing for 6 hours until the precipitation is complete; and (4) carrying out centrifugal separation on the precipitate, and washing, drying, grinding and calcining the obtained precipitate.
Solvents used for washing in the step (4) are deionized water and absolute ethyl alcohol, and washing is respectively carried out for three times; the drying temperature is 80 ℃, and the time is 10 hours; the calcination temperature is increased to 900 ℃ at the heating rate of 5 ℃/min for presintering for 2h, and then is increased to 1400 ℃ for sintering for 2h.
The magnesium-doped perovskite structure high-entropy ceramic electrode material is applied to the preparation of a super capacitor, and the preparation method of the super capacitor comprises the following steps:
(1) Uniformly mixing the magnesium-doped perovskite structure high-entropy ceramic electrode material, a conductive agent and a binder in an agate mortar, and grinding into fine slurry;
(2) Coating the uniformly mixed slurry on a 1X 1cm thick film 2 Drying the foamed nickel in an electrothermal blowing dry box at the temperature of 60 ℃ for more than or equal to 2 hours, and preparing a dried electrode slice into a working electrode under a tablet press;
(3) The prepared material is assembled into a super capacitor by using a three-electrode system, and then cyclic voltammetry test CV and constant current charge and discharge test GCD are carried out on the super capacitor.
In the step (1), the conductive agent is acetylene black, the binder is polyvinylidene fluoride (PVDF) dissolved in N-methyl pyrrolidone (NMP), and the concentration of the PVDF is 0.1 g/L; the mass ratio of the electrode material to the conductive agent to the adhesive is 75.
And (3) keeping the pressure of the tablet press in the step (2) at 10 MPa for 10 s.
The coprecipitation method used in the invention is simple and effective, and is convenient for large-scale application. The doped perovskite structure high-entropy ceramic can be successfully synthesized to be used as an electrode material by controlling the mass fraction of reactants, namely the proportion and the doping amount of each component of the perovskite structure high-entropy ceramic, the solution mixing and dissolving mode and sequence, the length of calcination time, the temperature and the like. Meanwhile, when the material is used as an electrode of a supercapacitor, the material can show the excellent characteristics of higher capacity, high multiplying power and long circulation, the performance of the maximum specific mass capacity can reach 652F/g multiplying power, and the capacity retention rate is still over 92% after 2000 circles of circulation.
Drawings
FIG. 1 shows Mg-doped Ba (CoCrFeMnNiMg) X ) 1/5+0.5 O 3-σ The X-ray diffraction pattern of the novel perovskite structure high-entropy ceramic material is compared with a standard PDF chart;
FIG. 2 shows Mg-doped Ba (CoCrFeMnNiMg) X ) 1/5+X O 3-σ X-ray diffraction pattern of the novel perovskite structure high-entropy ceramic material. Wherein the X-ray diffraction pattern comprises 6 different magnesium doping amounts, wherein X =0.3,0.4,0.5,0.6,0.7,0.8;
FIG. 3 shows the doping of Ba with Mg (CoCrFeMnNiMg) X ) 1/5+0.5 O 3-σ SEM microscopic structure chart of the novel perovskite structure high-entropy ceramic material;
FIG. 4 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different current densities X ) 1/5+0.4 O 3-σ The charge-discharge curve of the novel perovskite structure high-entropy ceramic material electrode;
FIG. 5 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different current densities X ) 1/5+0.5 O 3-σ The charge-discharge curve of the novel perovskite structure high-entropy ceramic material electrode;
FIG. 6 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different current densities X ) 1/5+0.6 O 3-σ The charge-discharge curve of the novel perovskite structure high-entropy ceramic material electrode;
FIG. 7 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different current densities X ) 1/5+0.7 O 3-σ The charge-discharge curve of the novel perovskite structure high-entropy ceramic material electrode;
FIG. 8 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different scan rates X ) 1/5+0.4 O 3-σ Cyclic voltammetry curve of novel perovskite structure high-entropy ceramic material electrode.
FIG. 9 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different scan rates X ) 1/5+0.5 O 3-σ Cyclic voltammetry curve of novel perovskite structure high entropy ceramic material electrode.
FIG. 10 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different scan rates X ) 1/5+0.6 O 3-σ Cyclic voltammetry curve of novel perovskite structure high entropy ceramic material electrode.
FIG. 11 shows the doping of Ba with Mg (CoCrFeMnNiMg) at different scan rates X ) 1/5+0.7 O 3-σ Cyclic voltammetry curve of novel perovskite structure high-entropy ceramic material electrode.
FIG. 12 shows different amounts of Mg-doped Ba (CoCrFeMnNiMg) X ) 1/5+X O 3-σ EIS diagram of novel perovskite structure high-entropy ceramic material, X =0.4,0.5,0.6,0.7 (EIS analysis is in frequency region of 10mHz to 10 kHz)And (6) rows. The fitted Nyquist plot shows that there is a diagonal line at low frequencies and no half circle at high frequencies. As shown in the inset, the equivalent circuit includes electrolyte solution resistance (Rs), interface faraday charge transfer resistance (Rct), warburg resistance (W σ), and capacitance (C). The lack of the semicircle indicates that the charge transfer resistance of the working electrode/electrolyte interface is low, and the charge diffusion between the electrolyte and the HEPO electrode is fast, which is caused by the mesoporous structure of the HEPO electrode);
FIG. 13 shows the doping of Ba with Mg at a current density of 1A/g (CoCrFeMnNiMg) X ) 1/5+0.5 O 3-σ The cycle performance curve of the novel perovskite structure high-entropy ceramic material electrode.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a magnesium-doped perovskite structure high-entropy ceramic electrode material is prepared by using Ba (CoCrFeMnNiMg) as high-entropy ceramic 0.3 ) 1/5.3 O 3-σ And σ is an oxygen vacancy.
The preparation method comprises the following steps: 3.4628g (Ba (NO) is weighed 3 ) 2 ）、0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.1525g（MgCl 2 ·6H 2 0) Dissolving deionized water in beaker to obtain solution A, adding 0.06mol of sodium carbonate as precipitant into 200ml of 0.3mol/L aqueous alkali to obtain solution B, and respectively placing solution A and solution B in beakerStirring for 2h on a magnetic stirrer.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The pellet was washed 3 times with deionized water and absolute ethanol, and removed from the centrifuge tube and placed in a glass dish. Drying in an oven at 80 deg.C for 10h to obtain precursor, grinding with agate mortar, presintering at 900 deg.C for 2h, and sintering at 1400 deg.C for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.3 ) 1/5.3 O 3-σ Placing the precursor in a high-temperature muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, presintering for 2h, then heating to 1400 ℃ and calcining for 2h, cooling to room temperature, testing the electrochemical specific capacity of the precursor through a three-electrode system, and measuring Ba (CoCrFeMnNiMg) under the current density of 1A/g 0.3 ) 1/5.3 O 3-σ The specific capacity of (A) was 456F/g.
Example 2: a magnesium-doped perovskite structure high-entropy ceramic electrode material is characterized in that: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) 0.4 ) 1/5.4 O 3-σ 。
The preparation method comprises the following steps: weigh 3.5281g (Ba (NO) 3 ) 2 ）、0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.2033g（MgCl 2 ·6H 2 0) Dissolving a proper amount of deionized water in a beaker to prepare a solution A, adding 200ml of 0.06mol of sodium carbonate as a precipitator to prepare an alkali solution with the total concentration of 0.3mol/L to obtain a solution B, and placing the solution A and the solution B on a magnetic stirrer to stir for 2 hours.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The pellet was washed 3 times with deionized water and absolute ethanol, and removed from the centrifuge tube and placed in a glass dish. Placing in a drying oven at 80 ℃ for more than 10h, drying to obtain a precursor, grinding the precursor by using an agate mortar, pre-sintering the precursor at 900 ℃ for 2h, and sintering the precursor at 1400 ℃ for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.4 ) 1/5.4 O 3-σ Placing the precursor in a high-temperature muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, presintering for 2h, then heating to 1400 ℃ and calcining for 2h, cooling to room temperature, testing the electrochemical specific capacity of the precursor through a three-electrode system, and measuring Ba (CoCrFeMnNiMg) under the current density of 1A/g 0.4 ) 1/5.4 O 3-σ The specific capacity of (A) was 554F/g.
Example 3: a high-entropy ceramic electrode material with a magnesium-doped perovskite structure is characterized in that: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) 0.5 ) 1/5.5 O 3-σ 。
The preparation method comprises the following steps: 3.5934g of barium nitrate (Ba (NO) was weighed 3 ) 2 ）、0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.2541g（MgCl 2 ·6H 2 0) Dissolving a proper amount of deionized water in a beaker to prepare a solution A, adding 200ml of 0.06mol of sodium carbonate as a precipitator to prepare an alkali solution with the total concentration of 0.3mol/L to obtain a solution B, and placing the solution A and the solution B on a magnetic stirrer to stir for 2 hours.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The precipitate was washed 3 times with deionized water and absolute ethanol, respectively, and removed from the centrifuge tube and placed in a glass dish. Placing in a drying oven at 80 ℃ for more than 10h, drying to obtain a precursor, grinding the precursor by using an agate mortar, pre-sintering the precursor at 900 ℃ for 2h, and sintering the precursor at 1400 ℃ for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.5 ) 1/5.5 O 3-σ The precursor is placed in a high-temperature muffle furnace, the temperature is raised to 900 ℃ at the rate of 5 ℃/min for presintering for 2h, then the temperature is raised to 1400 ℃ for calcining for 2h, the electrochemical specific capacity of the precursor is tested by a three-electrode system after the precursor is cooled to room temperature, and Ba (CoCrFeMnNiMg) is measured under the current density of 1A/g 0.5 ) 1/5.5 O 3-σ The specific capacity of (A) was 652F/g.
Example 4: a magnesium-doped perovskite structure high-entropy ceramic electrode material is characterized in that: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) 0.6 ) 1/5.6 O 3-σ 。
3.6588g (Ba (NO) was weighed) 3 ) 2 ）、0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.3050g（MgCl 2 ·6H 2 0) Dissolving a proper amount of deionized water in a beaker to prepare a solution A, adding 200ml of 0.06mol of sodium carbonate as a precipitator to prepare an alkali solution with the total concentration of 0.3mol/L to obtain a solution B, and placing the solution A and the solution B on a magnetic stirrer to stir for 2 hours.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The pellet was washed 3 times with deionized water and absolute ethanol, and removed from the centrifuge tube and placed in a glass dish. Putting the mixture into an oven at 80 ℃ for more than 10h, drying to obtain a precursor, grinding the precursor by using an agate mortar, presintering the precursor at 900 ℃ for 2h, and sintering the precursor at 1400 ℃ for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.6 ) 1/5.6 O 3-σ Placing the precursor in a high-temperature muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, presintering for 2h, then heating to 1400 ℃ and calcining for 2h, cooling to room temperature, testing the electrochemical specific capacity of the precursor through a three-electrode system, and measuring Ba (CoCrFeMnNiMg) under the current density of 1A/g 0.6 ) 1/5.6 O 3-σ Ratio of (A to (B)The capacity was 563F/g.
Example 5: a high-entropy ceramic electrode material with a magnesium-doped perovskite structure is characterized in that: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) 0.7 ) 1/5.7 O 3-σ 。
The preparation method comprises the following steps: 3.7241g of barium nitrate (Ba (NO) is weighed 3 ) 2 ）0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.3558g（MgCl 2 ·6H 2 0) Dissolving a proper amount of deionized water in a beaker to prepare a solution A, adding 200ml of 0.06mol of sodium carbonate serving as a precipitator into 200ml of aqueous alkali with the total concentration of 0.3mol/L to prepare a solution B, and placing the solution A and the solution B on a magnetic stirrer to stir for 2 hours.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The pellet was washed 3 times with deionized water and absolute ethanol, and removed from the centrifuge tube and placed in a glass dish. Placing in a drying oven at 80 ℃ for more than 10h, drying to obtain a precursor, grinding the precursor by using an agate mortar, pre-sintering the precursor at 900 ℃ for 2h, and sintering the precursor at 1400 ℃ for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.7 ) 1/5.7 O 3-σ Placing the precursor in a high-temperature muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, presintering for 2h, then heating to 1400 ℃ and calcining for 2h, cooling to room temperature, testing the electrochemical specific capacity of the precursor through a three-electrode system, and measuring Ba (CoCrFeMnNiMg) under the current density of 1A/g 0.7 ) 1/5.7 O 3-σ The specific capacity of (A) was 527F/g.
Example 6: a magnesium-doped perovskite structure high-entropy ceramic electrode material is characterized in that: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) 0.8 ) 1/5.8 O 3-σ 。
Weigh 3.7894g (Ba (NO) 3 ) 2 ）、0.7276g（Co(NO 3 ) 3 ·6H 2 0）、1.0003g（Cr(NO 3 ) 3 ·9H 2 0）、1.0100g（Fe(NO 3 ) 3 ·9H 2 0）、0.6276g（Mn(NO 3 ) 2 ·4H 2 0）、0.7270g（Ni(NO 3 ) 2 ·6H 2 0）、0.4066g（MgCl 2 ·6H 2 0) Dissolving a proper amount of deionized water in a beaker to prepare a solution A, adding 200ml of 0.06mol of sodium carbonate as a precipitator to prepare an alkali solution with the total concentration of 0.3mol/L to obtain a solution B, and placing the solution A and the solution B on a magnetic stirrer to stir for 2 hours.
Slowly adding the solution B into the solution A, and continuously stirring in the process until the precipitation is complete. Standing the precipitate for more than 6h, and separating the precipitate by using a centrifuge. The pellet was washed 3 times with deionized water and absolute ethanol, and removed from the centrifuge tube and placed in a glass dish. Placing in a drying oven at 80 ℃ for more than 10h, drying to obtain a precursor, grinding the precursor by using an agate mortar, pre-sintering the precursor at 900 ℃ for 2h, and sintering the precursor at 1400 ℃ for 2h.
Mixing Ba (CoCrFeMnNiMg) 0.8 ) 1/5.8 O 3-σ The precursor is placed in a high-temperature muffle furnace, the temperature is raised to 900 ℃ at the rate of 5 ℃/min for presintering for 2h, then the temperature is raised to 1400 ℃ for calcining for 2h, the electrochemical specific capacity of the precursor is tested by a three-electrode system after the precursor is cooled to room temperature, and Ba (CoCrFeMnNiMg) is measured under the current density of 1A/g 0.8 ) 1/5.8 O 3-σ The specific capacity of (A) is 485F/g.
The perovskite structure is characterized by: cations with larger radius, such as alkaline earth metal ions and rare earth element ions, are generally positioned at the A position, and the cations at the A position and oxygen ions are combined to form cubic stacking and play an important role in the stable existence of the perovskite structure; the cations in the B-position, which are generally of smaller radius, such as transition metal elements, are bound to oxygen atoms and are located in the octahedral centers in the cubic close packing. Cations at the A site and oxygen ions are combined to form cubic accumulation, and play an important role in the stable existence of a perovskite structure; the ions at the A site and the B site can be incompletely replaced by metal ions with the same radius generally, the original crystal structure is still maintained, new performance can be generated after the ions at the A site and the B site are incompletely replaced by other ions, and the variability of the performance enables the perovskite type composite oxide to meet the required characteristics of a supercapacitor material.
According to the above examples and the accompanying drawings, the obtained material has a specific capacity of 456F/g-652F/g, and when the doping capacity is 0.5, the specific capacity reaches the maximum 652F/g, but even when the doping capacity is 0.3, the specific capacity is higher than 456F/g, the retention rate of the cycle performance after 2000 cycles of testing is higher than 90%, and the performance of large multiplying power and long cycle is reflected.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The method for preparing the high-entropy ceramic electrode material with the magnesium-doped perovskite structure is characterized by comprising the following steps of: the magnesium-doped perovskite structure high-entropy ceramic is Ba (CoCrFeMnNiMg) X ) 1/（5+X） O 3-σ Wherein: x =0.3,0.4,0.5,0.6,0.7,0.8; σ is an oxygen vacancy;
the preparation method is characterized by adopting a coprecipitation method for synthesis, and comprises the following specific steps:
(1) Dissolving barium nitrate Ba (NO 3) 2, cobalt nitrate hexahydrate Co (NO 3) 3.6H 20, chromium nitrate nonahydrate Cr (NO 3) 3.9H 20, ferric nitrate nonahydrate Fe (NO 3) 3.9H 20, manganese nitrate tetrahydrate Mn (NO 3) 2.4H 20, nickel nitrate hexahydrate Ni (NO 3) 2.6H 20 and magnesium chloride hexahydrate MgCl 2.6H 20 in deionized water, and uniformly mixing to obtain a clear solution A; wherein: the mol ratio of Ba (NO 3) 2, co (NO 3) 3 & 6H20, cr (NO 3) 3 & 9H20, fe (NO 3) 3 & 9H20, mn (NO 3) 2 & 4H20, ni (NO 3) 2 & 6H20, mgCl2 & 6H20 is 5+ X:1:1:1:1:1: x, wherein: x =0.3,0.4,0.5,0.6,0.7,0.8;
(2) Adding 0.06mol of sodium carbonate into 200ml of aqueous alkali with the total concentration of 0.3mol/L, and uniformly stirring to obtain a clear solution B;
(3) Respectively placing the solution A and the solution B on a magnetic stirrer and stirring for 2 hours;
(4) Adding the solution B obtained in the step (3) into the solution A while stirring, and standing for 6 hours until the precipitation is complete; and (4) carrying out centrifugal separation on the precipitate, washing, drying, grinding and calcining the obtained precipitate.
2. The method for preparing a high-entropy ceramic electrode material with a magnesium-doped perovskite structure according to claim 1, characterized in that: solvents used for washing in the step (4) are deionized water and absolute ethyl alcohol, and washing is respectively carried out for three times; the drying temperature is 80 ℃, and the drying time is 10 hours; the calcination temperature is increased to 900 ℃ at the heating rate of 5 ℃/min for presintering for 2h, and then is increased to 1400 ℃ for sintering for 2h.
3. The application of the magnesium-doped perovskite-structured high-entropy ceramic electrode material obtained by the preparation method of claim 1 in preparing a supercapacitor is characterized in that: the preparation method of the super capacitor comprises the following steps:
(1) Uniformly mixing the magnesium-doped perovskite structure high-entropy ceramic electrode material, a conductive agent and a binder in an agate mortar, and grinding into fine slurry;
(2) Coating the uniformly mixed slurry on a 1X 1cm thick film 2 Drying the foamed nickel in an electrothermal blowing dry box at the temperature of 60 ℃ for more than or equal to 2 hours, and preparing a dried electrode slice into a working electrode under a tablet press;
(3) The prepared material is assembled into a super capacitor by using a three-electrode system, and then cyclic voltammetry test CV and constant current charge and discharge test GCD are carried out on the super capacitor.
4. The application of the magnesium-doped perovskite structure high-entropy ceramic electrode material in the preparation of the supercapacitor according to claim 3 is characterized in that: in the step (1), the conductive agent is acetylene black, the binder is polyvinylidene fluoride (PVDF) dissolved in N-methylpyrrolidone (NMP), and the concentration of the PVDF is 0.1 g/L; the mass ratio of the electrode material to the conductive agent to the adhesive is 75.
5. The application of the magnesium-doped perovskite structure high-entropy ceramic electrode material in the preparation of the supercapacitor is characterized in that: and (3) keeping the pressure of the tablet press in the step (2) at 10 MPa for 10 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110824273.8A CN113658808B (en) | 2021-07-21 | 2021-07-21 | Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110824273.8A CN113658808B (en) | 2021-07-21 | 2021-07-21 | Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113658808A CN113658808A (en) | 2021-11-16 |
| CN113658808B true CN113658808B (en) | 2023-02-03 |
Family
ID=78477623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110824273.8A Active CN113658808B (en) | 2021-07-21 | 2021-07-21 | Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113658808B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115050978A (en) * | 2022-06-23 | 2022-09-13 | 电子科技大学 | High-entropy solid oxide fuel cell and preparation and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007012284A (en) * | 2005-06-28 | 2007-01-18 | Toshiba Corp | Electrode catalyst, manufacturing method thereof, fuel electrode, and fuel cell apparatus |
| JP2009208979A (en) * | 2008-03-03 | 2009-09-17 | Murata Mfg Co Ltd | Dielectric ceramic and multilayer ceramic capacitor |
| CN104538206A (en) * | 2014-12-12 | 2015-04-22 | 南京工业大学 | Application of perovskite oxide in super capacitor |
| CN110467227A (en) * | 2019-09-19 | 2019-11-19 | 安徽工业大学 | The high entropy oxide material of novel Ca-Ti ore type and preparation method of the high entropy in five yuan of the position B |
| CN110526706A (en) * | 2019-09-19 | 2019-12-03 | 安徽工业大学 | A kind of high entropy oxide powder material of eutectic and preparation method |
| CN110563462A (en) * | 2019-09-19 | 2019-12-13 | 安徽工业大学 | B-site six-element high-entropy novel perovskite type high-entropy oxide material and preparation method thereof |
| CN110845237A (en) * | 2019-11-28 | 2020-02-28 | 太原理工大学 | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block |
| CN111362683A (en) * | 2020-03-10 | 2020-07-03 | 南昌航空大学 | Hexahydric spinel type iron-cobalt-chromium-manganese-magnesium-nickel high-entropy oxide and powder preparation method thereof |
| CN112723862A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Method for preparing high-entropy oxide ceramic material simply and low in consumption |
| CN112811891A (en) * | 2020-12-26 | 2021-05-18 | 重庆材料研究院有限公司 | Spinel phase high-entropy thermistor material and preparation method thereof |
-
2021
- 2021-07-21 CN CN202110824273.8A patent/CN113658808B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007012284A (en) * | 2005-06-28 | 2007-01-18 | Toshiba Corp | Electrode catalyst, manufacturing method thereof, fuel electrode, and fuel cell apparatus |
| JP2009208979A (en) * | 2008-03-03 | 2009-09-17 | Murata Mfg Co Ltd | Dielectric ceramic and multilayer ceramic capacitor |
| CN104538206A (en) * | 2014-12-12 | 2015-04-22 | 南京工业大学 | Application of perovskite oxide in super capacitor |
| CN110467227A (en) * | 2019-09-19 | 2019-11-19 | 安徽工业大学 | The high entropy oxide material of novel Ca-Ti ore type and preparation method of the high entropy in five yuan of the position B |
| CN110526706A (en) * | 2019-09-19 | 2019-12-03 | 安徽工业大学 | A kind of high entropy oxide powder material of eutectic and preparation method |
| CN110563462A (en) * | 2019-09-19 | 2019-12-13 | 安徽工业大学 | B-site six-element high-entropy novel perovskite type high-entropy oxide material and preparation method thereof |
| CN110845237A (en) * | 2019-11-28 | 2020-02-28 | 太原理工大学 | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block |
| CN111362683A (en) * | 2020-03-10 | 2020-07-03 | 南昌航空大学 | Hexahydric spinel type iron-cobalt-chromium-manganese-magnesium-nickel high-entropy oxide and powder preparation method thereof |
| CN112811891A (en) * | 2020-12-26 | 2021-05-18 | 重庆材料研究院有限公司 | Spinel phase high-entropy thermistor material and preparation method thereof |
| CN112723862A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Method for preparing high-entropy oxide ceramic material simply and low in consumption |
Non-Patent Citations (2)
| Title |
|---|
| A high entropy oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) with superior lithium storage performance;Nan Qiu etc;《Journal of Alloys and Compounds》;20181106;第777卷;第768页左栏第1段，770页右栏第2段，773页左栏第2段 * |
| La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 钙钛矿高熵陶瓷粉体的制备及其电学性能;郭猛等;《无机材料学报》;20201105;第36 卷(第4 期);第432页左栏最后1段，第433页第2段，435页最后1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113658808A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108923042B (en) | Layered manganese-based positive electrode material of sodium-ion battery and preparation method thereof | |
| WO2023097984A1 (en) | Positive electrode material and preparation method therefor, positive electrode plate, and sodium ion battery | |
| CN102916169B (en) | Lithium-rich manganese-based anode material and method for manufacturing same | |
| CN104051724A (en) | Carbon-coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN108461719A (en) | It is a kind of richness lithium material/conductive organic polymer composite positive pole and electrode preparation method | |
| CN114566632B (en) | Positive electrode material for sodium ion battery and preparation method thereof | |
| WO2014169717A1 (en) | Electrochemical energy storage device of aqueous alkali metal ions | |
| CN106935828A (en) | A kind of modified height ratio capacity positive electrode and preparation method thereof | |
| CN113690430A (en) | Lithium-rich manganese-based positive electrode material for realizing accurate lithium preparation and preparation method and application thereof | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN110416521A (en) | A kind of sodium-ion battery tertiary cathode material and preparation method thereof of magnesium doping | |
| CN111762820A (en) | Layered manganese-based positive electrode material of sodium-ion battery and preparation method thereof | |
| Jin et al. | The influence of Ni doping on the structure and electrochemical properties of LiCoO2 materials | |
| CN105932241A (en) | Preparation method of nickel-cobalt-lithium aluminate composite positive electrode material | |
| CN115863626A (en) | O3 type high-entropy sodium ion battery positive electrode material, preparation method thereof and application thereof in sodium ion battery | |
| CN104241628B (en) | A kind of preparation method and its obtained product and purposes of the di-iron trioxide microballoon of titanium dioxide modification | |
| CN104681799A (en) | Method for manufacturing lithium iron manganese phosphate/carbon cathode material and application thereof | |
| CN113658808B (en) | Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor | |
| CN103326014A (en) | Manganese-series layered lithium-rich cathode material, preparation method thereof and applications thereof | |
| CN108987125B (en) | Perovskite stannate supercapacitor electrode material, preparation method and application | |
| CN103855372A (en) | High-manganese composite cathode material and preparation method thereof | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN112408490A (en) | Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material | |
| CN116081710A (en) | Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof | |
| CN107591530B (en) | Modification method of lithium titanate negative electrode material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |