CN114784241A - Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
- Publication number
- CN114784241A CN114784241A CN202210385588.1A CN202210385588A CN114784241A CN 114784241 A CN114784241 A CN 114784241A CN 202210385588 A CN202210385588 A CN 202210385588A CN 114784241 A CN114784241 A CN 114784241A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- sodium
- electrode material
- ion battery
- formula
- 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.)
- Granted
Links
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 62
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910014248 MzO2 Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 50
- 238000005245 sintering Methods 0.000 claims description 46
- 239000011343 solid material Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 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 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- -1 prussian blue compound Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910018948 NaNi0.5Ti0.5O2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion battery manufacturing, and discloses a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery. The molecular formula of the anode material is NaNixTiyMzO2Formula (1); in the formula (1), M element is selected from one of Fe, V, Sn, Mo, Cr and Cu; the M element comprises a lower valence M element and a higher valence M element, and the content molar ratio of the lower valence M element to the higher valence M element is 1: 0.1-10; x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98; placing the anode material at a humidity of 10-30 wt%And the change value of the pH value of the surface of the positive electrode material is not more than 0.01 after 10 days in the environment. The sodium ion battery prepared by the anode material provided by the invention has excellent cycle stability and storage performance.
Description
Technical Field
The invention relates to the technical field of sodium ion battery manufacturing, in particular to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
Currently, with the continuous development of new energy industries, people pay attention to energy storage density and urgently need to reduce the cost of raw materials; due to the global uneven distribution of lithium resources, the price of raw materials such as lithium-containing ores is increasing continuously in recent years, so that the manufacturing cost of batteries is increasing continuously, and the continuous development of new energy industries is seriously hindered.
Wherein, sodium and lithium are positioned in the same main group, the resource is very rich, and the sodium and the lithium have similar physicochemical properties; when the material is prepared into a corresponding electrode material, the material shows the same properties with the positive electrode material of the lithium ion battery, and becomes one of the first choice for replacing the lithium ion battery.
Sodium ion batteries have a great potential advantage: the sodium salt raw material has rich reserves and low price; na (Na)+The electrolyte can be migrated and transported at low concentration; na (Na)+The anode does not react with aluminum, and cheap aluminum foil can be used as an electrode material; because the sodium ion battery has the characteristic of no need of over-discharging, the sodium ion battery is allowed to discharge to zero volt, so that the energy density of the sodium ion battery is greatly improved。
In the whole sodium ion battery, the capacity and voltage of the positive electrode material directly influence the energy density of the system, and the cost of the positive electrode material is dominant, so that the seeking of the positive electrode material with stable structure, excellent performance and low price is the key for developing the sodium ion battery.
The existing sodium ion batteries mainly comprise three types: layered oxides, polyanionic compounds and prussian blue compounds.
The polyanionic compound has a three-dimensional framework structure and abundant sodium ion de-intercalation channels, and has the advantages of high working voltage (>3.5V), good power performance and good cycle stability (more than ten thousand times). However, the vanadium-based raw materials are generally sintered at high temperature, so that the cost is reduced by simplifying the synthesis method, and a reasonable solution strategy is needed for solving the problem of poor material conductivity.
The discharge capacity and the working voltage of the prussian blue compound are moderate and not prominent enough, and interlayer water occupies the potential of sodium ions, so that the electrochemical reaction is seriously influenced.
The layered oxide material has high reversible specific capacity and ideal electronic conductance, and is mainly divided into two types according to the structural characteristics: type O3 and type P2. The P2 material has low capacity and good rate capability, but the matching difficulty of the full cell is larger due to the limitation of sodium content in the crystal structure. The O3 material has high capacity and good commercial application prospect.
CN109449418A discloses a composite sodium ion anode material with a core-shell structure and a preparation method thereof, the scheme is that a core-shell structure is constructed by adopting a secondary sintering method, and the problem of poor storage stability is solved, but the secondary sintering method is high in energy consumption, and the problem of poor cycle stability of a sodium ion battery caused by serious sodium ion loss after multiple sintering is solved.
CN112968165A discloses a modified sodium ion positive electrode material, a modified sodium ion electrode and a preparation method thereof, in the scheme, fluorine ions are introduced to replace oxygen ions, so as to perform a modification function, but the obtained positive electrode material still has the problems of poor storage stability and sodium ion loss, so that the obtained sodium ion battery has poor cycle performance.
Therefore, how to develop the positive electrode material of the sodium-ion battery with good storage stability in air and good cycle performance has great significance for developing the sodium-ion battery.
Disclosure of Invention
The invention aims to solve the problems of poor storage stability and poor cycle stability of a sodium ion positive electrode material in the prior art.
In order to achieve the above object, the present invention provides a positive electrode material for sodium ion battery, which is characterized in that the formula of the positive electrode material is NaNixTiyMzO2Formula (1);
in the formula (1), M element is selected from one of Fe, V, Sn, Mo, Cr and Cu; the M element comprises a lower valence M element and a higher valence M element, and the content molar ratio of the lower valence M element to the higher valence M element is 1: 0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
and (3) placing the positive electrode material in an environment with the humidity of 10-30 wt% for 10 days, wherein the change value of the pH value on the surface of the positive electrode material is not more than 0.01.
Preferably, the content molar ratio of the lower-valence M element to the higher-valence M element is 1: 1-10.
Preferably, in formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85.
In a second aspect, the present invention provides a method for preparing the sodium ion positive electrode material of the first aspect, which comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide and an oxide containing M element to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar usage of the sodium carbonate calculated by sodium element is the sum of the initial usage a and the supplement usage k;
(2) in the presence of a solvent, carrying out second contact mixing on the first solid material and an auxiliary A to obtain a second solid material, and drying the second solid material; the A auxiliary agent is at least one of phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is greater than 0, and k is calculated according to a formula shown in formula (2);
k＝[(2.18T1×t+(T1-T0)2]/121680V, formula (2);
in formula (2), T0Represents the initial temperature, deg.C, of the sintering process;
T1represents the sintering treatment temperature, DEG C;
t represents the heat preservation time of the sintering treatment, h;
v represents the temperature increase rate of the sintering treatment, min.
Preferably, in step (1), the nickel oxide is used in an amount of (0.01-0.3) a moles, the titanium dioxide is used in an amount of (0.01-0.3) a moles, and the M element-containing oxide is used in an amount of (0.4-0.98) a moles, with respect to the initial amount a moles of the sodium carbonate in terms of sodium element.
Preferably, in step (1), the conditions of the sintering treatment include at least: the heating rate is 2-5 ℃/min, the temperature is 800-.
Preferably, in the step (2), the A auxiliary agent is used in an amount of 2-5 wt% based on the total weight of the first solid material.
Preferably, in step (2), the conditions of the second contact mixing at least include: the temperature is 20-40 ℃, and the time is 2-6 h.
Preferably, in step (2), the conditions of the drying treatment include at least: the temperature is 100 ℃ and 150 ℃, and the time is 2-4 h.
The third aspect of the present invention provides a sodium ion battery, in which the positive electrode material is the positive electrode material of the sodium ion battery described in the first aspect.
The sodium ion battery prepared by the positive electrode material provided by the invention has excellent cycling stability and storage performance, particularly, the capacity retention rate of the sodium ion battery obtained by the invention is improved, and the discharge specific capacity is still kept above 92% after 100 cycles of cycling.
Drawings
Fig. 1 is a graph showing the cycle capacity of batteries formed of the positive electrode materials prepared in example 1 of the present invention and comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the room temperature or the room temperature both represent 25. + -. 2 ℃.
The invention provides a sodium ion battery anode material, which is characterized in that the molecular formula of the anode material is NaNixTiyMzO2Formula (1);
in the formula (1), M element is selected from one of Fe, V, Sn, Mo, Cr and Cu; the M element comprises a lower valence M element and a higher valence M element, and the content molar ratio of the lower valence M element to the higher valence M element is 1: 0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
and (3) placing the positive electrode material in an environment with the humidity of 10-30 wt% for 10 days, wherein the change value of the pH value on the surface of the positive electrode material is not more than 0.01.
In the present invention, the "lower valence M element and the higher valence M element" refer to that the positive electrode material contains both lower valence and higher valence of the same element, and exemplarily, when the M element is copper, the positive electrode material may contain both of + 1-valent cuprous ion and + 2-valent cupric ion; when the M element is iron, the positive electrode material may contain ferrous ions having a valence of +2 and ferric ions having a valence of + 3.
Preferably, the content molar ratio of the lower-valence M element to the higher-valence M element is 1: 1-10. The inventors found that, in this preferred case, a sodium ion battery more excellent in cycle stability and storage stability can be obtained.
Preferably, in formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85. The inventors have found that in this preferred embodiment, a sodium ion battery is obtained having more excellent electrochemical performance.
In a second aspect, the present invention provides a method for preparing the sodium ion positive electrode material of the first aspect, which comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide and an oxide containing M element to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar usage of the sodium carbonate is the sum of the initial usage a and the supplement usage k;
(2) in the presence of a solvent, carrying out second contact mixing on the first solid material and an A auxiliary agent to obtain a second solid material, and drying the second solid material; the A auxiliary agent is selected from at least one of phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is greater than 0, and k is calculated according to a formula shown in formula (2);
k＝[(2.18T1×t+(T1-T0)2]/121680V, formula (2);
in formula (2), T0Represents the initial temperature, deg.C, of the sintering process;
T1represents the sintering treatment temperature, DEG C;
t represents the heat preservation time of the sintering treatment, h;
v represents the temperature increase rate of the sintering treatment, min.
The inventor finds that the preparation method provided by the invention can accurately supplement the using amount of sodium carbonate and avoid the problem of poor battery cycle performance caused by sodium ion loss in the research process.
Preferably, in step (1), the nickel oxide is used in an amount of (0.01-0.3) a moles, the titanium oxide is used in an amount of (0.01-0.3) a moles, and the M element-containing oxide is used in an amount of (0.4-0.98) a moles, relative to the initial amount a moles of the sodium carbonate in terms of sodium element.
Preferably, in step (1), the conditions of the first contact mixing include at least: the temperature is 20-40 ℃, and the time is 2-6 h.
Preferably, in step (1), the conditions of the sintering treatment include at least: the heating rate is 2-5 ℃/min, the temperature is 800-950 ℃, and the heat preservation time is 2-30 h. More preferably, in step (1), the conditions of the sintering treatment include at least: the heating rate is 2-5 ℃/min, the temperature is 800-900 ℃, and the heat preservation time is 5-24 h. The inventor finds that the specific implementation mode in the preferable case can effectively reduce the energy consumption on the premise of ensuring the cycling stability of the sodium-ion battery.
Preferably, in the step (2), the A aid accounts for 2-5 wt% of the total weight of the first solid material. The inventors found that with this embodiment in the preferred case, a sodium ion battery having more excellent cycle stability and storage stability was obtained.
Preferably, in step (2), the conditions of the second contact mixing at least include: the temperature is 20-40 ℃ and the time is 2-3.5 h.
Preferably, in step (2), the conditions of the drying treatment include at least: the temperature is 100-150 ℃, and the time is 2-4 h.
The third aspect of the present invention provides a sodium ion battery, in which the positive electrode material is the positive electrode material of the sodium ion battery described in the first aspect.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
And (3) auxiliary agent A: ammonium fluoride, available from aladine pharmaceutical;
in the following examples, sodium carbonate, nickel oxide, titanium dioxide, copper oxide, cuprous oxide, ferric oxide, ferrous oxide, and ethanol were all analytical chemicals.
Example 1
The embodiment provides a method for preparing a positive electrode material of a sodium-ion battery, which comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide according to a molar ratio of 1.03:0.15:0.15:0.45:0.375 (wherein the initial dosage of the sodium carbonate calculated by sodium element is 1 mol, and the supplementary dosage is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein the conditions of the first contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 h;
(2) dissolving 3.51g of an A aid (accounting for 3 wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material, carrying out second contact mixing to obtain a second solid material, and drying the second solid material to obtain a sodium-ion battery cathode material NaNi0.15Ti0.15Fe0.825O2；
Wherein the second contact mixing conditions are as follows: the temperature is room temperature and the time is 2 hours;
the conditions of the drying treatment were: the temperature is 120 ℃ and the time is 2 h.
Example 2
The embodiment provides a method for preparing a positive electrode material of a sodium-ion battery, which comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide according to a molar ratio of 1.03:0.3:0.3:0.25:0.225 (wherein the initial dosage of the sodium carbonate calculated by sodium element is 1 mol, and the supplementary dosage is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein the conditions of the first contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 h;
(2) dissolving 3.41g of an auxiliary A (accounting for 3 wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material, carrying out second contact mixing to obtain a second solid material, and drying the second solid material to obtain a sodium-ion battery cathode material NaNi0.3Ti0.3Fe0.475O2；
Wherein the conditions of the second contact mixing are as follows: the temperature is room temperature, and the time is 2 h;
the conditions of the drying treatment were: the temperature is 120 ℃ and the time is 2 h.
Example 3
The embodiment provides a method for preparing a positive electrode material of a sodium-ion battery, which comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide according to a molar ratio of 1.03:0.15:0.15:0.4:0.45 (wherein the initial dosage of the sodium carbonate calculated by sodium element is 1 mol, and the supplementary dosage is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein the conditions of the first contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 5 ℃/min, the sintering treatment temperature is 800 ℃, and the heat preservation time is 20 h;
(2) dissolving 5.92g of an auxiliary A (accounting for 5 wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material, carrying out second contact mixing to obtain a second solid material, and drying the second solid material to obtain a sodium-ion battery cathode material NaNi0.15Ti0.15Fe0.85O2；
Wherein the conditions of the second contact mixing are as follows: the temperature is room temperature, and the time is 2 h;
the conditions of the drying treatment were: the temperature is 150 ℃ and the time is 2 h.
Example 4
A sodium ion positive electrode material was prepared by the method of example 1, except that, in step (1), sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide were used in a molar ratio of 1.03:0.1:0.1:0.5:0.45 (wherein sodium carbonate was used in an initial amount of 1 mole and a supplementary amount of 0.03 mole, based on sodium element).
The rest steps are the same as the example 1, and the positive electrode material NaNi of the sodium-ion battery is obtained0.15Ti0.15Fe0.95O2。
Comparative example 1
A method for producing a sodium ion positive electrode material according to the method of example 1, except that the step (2) is not carried out;
the method specifically comprises the following steps:
performing first contact mixing on sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide according to a molar ratio of 1.03:0.15:0.15:0.45:0.375 (wherein the initial dosage of the sodium carbonate calculated by sodium element is 1 mol, and the supplementary dosage is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a sodium-ion battery anode material NaNi0.15Ti0.15Fe0.825O2；
Wherein the conditions of the first contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 h.
Comparative example 2
A method for preparing a sodium ion positive electrode material according to the method of example 1, except that, in step (1), iron oxide and ferrous oxide were not added;
the method specifically comprises the following steps:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide and titanium dioxide according to a molar ratio of 1.03:0.5:0.5 (wherein the initial using amount of the sodium carbonate calculated by sodium element is 1 mol, and the supplementary using amount is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein the conditions of the first contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 h;
(2) dissolving 3.25g of an auxiliary A (accounting for 3 wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material, carrying out second contact mixing to obtain a second solid material, and drying the second solid material to obtain a sodium-ion battery cathode material NaNi0.5Ti0.5O2；
Wherein the conditions of the second contact mixing are as follows: the temperature is room temperature, and the time is 4 h;
the conditions of the drying treatment were: the temperature is 120 ℃ and the time is 2 h.
Comparative example 3
A method for producing a sodium ion positive electrode material according to the method of example 1, except that, in step (1), sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide are first contact-mixed in a molar ratio of 1.03:0.215:0.28:0.05:0.65 (wherein the initial amount of sodium carbonate in terms of sodium element is 1 mole, and the supplementary amount is 0.03 mole) to obtain a first mixture, and the first mixture is subjected to a sintering treatment to obtain a first solid material;
wherein the conditions of the first contact mixing are as follows: the temperature is room temperature and the time is 4 hours;
the conditions of the sintering treatment are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 h;
(2) dissolving 3.60g of the additive A (accounting for 3 wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material, carrying out second contact mixing to obtain a second solid material, and drying the second solid material to obtain sodiumAnode material NaNi of ion battery0.215Ti0.28Fe0.7O2；
Wherein the second contact mixing conditions are as follows: the temperature is room temperature and the time is 4 hours;
the conditions of the drying treatment were: the temperature is 120 ℃ and the time is 2 h.
Test example 1
The positive electrode materials (5g) in the examples and comparative examples were respectively dissolved in 100g of deionized water to obtain suspensions, and then the suspensions were tested using a pH meter (mettlerlitosan S400-K) to obtain pH values; the positive electrode material was placed in a space with a humidity of 20%, and after 10 days, the pH was again measured by the method described above, and the specific test results are shown in table 1.
TABLE 1
| Example numbering | Day one | After 10 days |
| Example 1 | 10.32 | 10.33 |
| Example 2 | 10.38 | 10.37 |
| Example 3 | 10.35 | 10.36 |
| Example 4 | 10.33 | 10.33 |
| Comparative example 1 | 12.08 | 12.82 |
| Comparative example 2 | 10.67 | 10.68 |
| Comparative example 3 | 10.37 | 10.36 |
The results in table 1 show that the surface pH of the positive electrode material prepared by the method is decreased, and the surface pH changes by only 0.01 after ten days; while comparative example 1 changed by 0.74 after ten days, indicating that the surface of the cathode material prepared in comparative example 1 had chemically reacted with air.
Test example 2
The positive electrode materials prepared in the binder PTFE, the conductive carbon black, the examples and the comparative examples are fully mixed and coated on an aluminum foil according to the mass ratio of 1:2:7 to obtain a pole piece loaded with an active substance, and the loading amount is controlled to be 6mg/cm2The cut pole piece (diameter is 12mm) is subjected to vacuum (vacuum degree is 133Pa) heat preservation for 6h at 120 ℃, and is transferred into a glove box (the content of water and oxygen is less than 0.01ppm) filled with argon after being cooled to room temperature, and a CR2032 battery is sequentially assembled by taking a sodium piece as a half-battery cathode, taking sodium perchlorate as electrolyte and taking glass fiber as a diaphragm.
Wherein, the charging and discharging test conditions are as follows: the working voltage range is set to be 2V-4.2V, circulation is carried out at the multiplying power of 1C, the discharge specific capacity of the 1 st circle, the 10 th circle, the 50 th circle and the 100 th circle is recorded respectively after one hundred circles of circulation, the capacity retention rate is calculated, and specific test results are shown in table 2.
Capacity retention ratio 1: (discharge specific capacity at 10 th cycle/discharge specific capacity at 1 st cycle) × 100%;
capacity retention ratio 2: (discharge specific capacity at 50 th circle/discharge specific capacity at 1 st circle) x 100%;
capacity retention ratio 3: (specific discharge capacity at 100 th cycle/specific discharge capacity at 1 st cycle) × 100%.
TABLE 2
The results in table 2 show that the sodium ion battery formed by the positive electrode material prepared by the method of the present invention has more excellent specific discharge capacity and capacity retention rate.
The present invention exemplarily provides a cycle capacity map of a battery formed using the cathode materials prepared in example 1 and comparative example 1, see fig. 1.
As can be seen from fig. 1, the battery prepared from the positive electrode material provided by the invention has more excellent specific discharge capacity and capacity retention rate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The positive electrode material of the sodium-ion battery is characterized in that the molecular formula of the positive electrode material is shown as a formula (1);
NaNixTiyMzO2formula (1);
in the formula (1), M element is selected from any one of Fe, V, Sn, Mo, Cr and Cu; the M element comprises a lower valence M element and a higher valence M element, and the content molar ratio of the lower valence M element to the higher valence M element is 1: 0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
the positive electrode material is placed in an environment with the humidity of 10-30 wt% for 10 days, and the change value of the pH value on the surface of the positive electrode material is no more than 0.01.
2. The positive electrode material as claimed in claim 1, wherein the molar ratio of the lower-valence M element to the higher-valence M element is 1: 1-10.
3. The positive electrode material according to claim 1 or 2, wherein in formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85.
4. A method for preparing the sodium ion positive electrode material according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) carrying out first contact mixing on sodium carbonate, nickel oxide, titanium dioxide and an oxide containing M element to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar usage of the sodium carbonate calculated by sodium element is the sum of the initial usage a and the supplement usage k;
(2) in the presence of a solvent, carrying out second contact mixing on the first solid material and an A auxiliary agent to obtain a second solid material, and drying the second solid material; the A auxiliary agent is at least one of phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is larger than 0, and k is calculated according to a formula shown in a formula (2);
k＝[(2.18T1×t+(T1-T0)2]/121680V, formula (2);
in formula (2), T0Represents the initial temperature, deg.C, of the sintering process;
T1represents the sintering temperature, ° c;
t represents the heat preservation time of the sintering treatment, h;
v represents the temperature increase rate of the sintering treatment, min.
5. The process according to claim 4, wherein in step (1), the nickel oxide is used in an amount of (0.01-0.3) a moles, the titanium oxide is used in an amount of (0.01-0.3) a moles, and the M element-containing oxide is used in an amount of (0.4-0.98) a moles, relative to a moles of the sodium carbonate in terms of sodium element.
6. The method according to claim 4 or 5, wherein in step (1), the conditions of the sintering process comprise at least: the heating rate is 2-5 ℃/min, the temperature is 800-.
7. The method according to any one of claims 4 to 6, wherein in step (2), the amount of the A aid is 2 to 5 wt% based on the total weight of the first solid material.
8. The method according to any one of claims 4 to 7, wherein in step (2), the conditions of the second contacting and mixing at least comprise: the temperature is 20-40 ℃ and the time is 2-6 h.
9. The method according to any one of claims 4 to 8, wherein in step (2), the conditions of the drying treatment include at least: the temperature is 100-150 ℃, and the time is 2-4 h.
10. A sodium-ion battery, characterized in that the positive electrode material in the sodium-ion battery is the positive electrode material for a sodium-ion battery according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385588.1A CN114784241B (en) | 2022-04-13 | 2022-04-13 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385588.1A CN114784241B (en) | 2022-04-13 | 2022-04-13 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114784241A true CN114784241A (en) | 2022-07-22 |
| CN114784241B CN114784241B (en) | 2023-11-28 |
Family
ID=82429937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210385588.1A Active CN114784241B (en) | 2022-04-13 | 2022-04-13 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114784241B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125069A (en) * | 2022-08-12 | 2022-09-30 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium-ion battery and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456936A (en) * | 2012-05-31 | 2013-12-18 | 中国科学院物理研究所 | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance |
| US20150129797A1 (en) * | 2013-11-08 | 2015-05-14 | Kabushiki Kaisha Toshiba | Production method of battery active material, battery active material, nonaqueous electrolyte battery and battery pack |
| CN106673075A (en) * | 2017-01-03 | 2017-05-17 | 中国科学院化学研究所 | Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof |
| CN107093713A (en) * | 2017-04-07 | 2017-08-25 | 武汉大学 | A kind of anion doped sodium-ion battery oxide anode material |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN108039458A (en) * | 2017-11-15 | 2018-05-15 | 中南大学 | A kind of sodium-ion battery positive material and its preparation method and application |
| CN109830679A (en) * | 2019-02-01 | 2019-05-31 | 中国科学院过程工程研究所 | A kind of positive electrode material precursor, and its preparation method and application |
| CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
| CN112299487A (en) * | 2019-07-30 | 2021-02-02 | 北京大学 | All-manganese or high-manganese-based lithium-rich layered cathode material with disordered cations in layer and preparation method thereof |
| CN113078298A (en) * | 2020-01-06 | 2021-07-06 | 中国科学院物理研究所 | Sodium-magnesium-iron-manganese-based layered oxide material, preparation method and application |
| CN113258060A (en) * | 2020-02-11 | 2021-08-13 | 中国科学院物理研究所 | Sodium ion battery high-nickel layered oxide material and preparation method and application thereof |
| CN113629299A (en) * | 2021-07-12 | 2021-11-09 | 河北光兴半导体技术有限公司 | Solid-state battery and preparation process thereof |
| CN113964304A (en) * | 2021-10-20 | 2022-01-21 | 吕宜媛 | Doped layered positive electrode material and preparation method thereof |
| CN114132971A (en) * | 2021-11-26 | 2022-03-04 | 西安交通大学 | Sodium ion battery positive electrode material with composite symbiotic structure, preparation method and sodium ion battery |
| CN114229918A (en) * | 2021-12-20 | 2022-03-25 | 北京化工大学 | Method for regulating phase proportion in positive electrode material of sodium-ion battery, preparation and application thereof |
-
2022
- 2022-04-13 CN CN202210385588.1A patent/CN114784241B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456936A (en) * | 2012-05-31 | 2013-12-18 | 中国科学院物理研究所 | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance |
| US20150129797A1 (en) * | 2013-11-08 | 2015-05-14 | Kabushiki Kaisha Toshiba | Production method of battery active material, battery active material, nonaqueous electrolyte battery and battery pack |
| CN106673075A (en) * | 2017-01-03 | 2017-05-17 | 中国科学院化学研究所 | Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof |
| CN107093713A (en) * | 2017-04-07 | 2017-08-25 | 武汉大学 | A kind of anion doped sodium-ion battery oxide anode material |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN108039458A (en) * | 2017-11-15 | 2018-05-15 | 中南大学 | A kind of sodium-ion battery positive material and its preparation method and application |
| CN109830679A (en) * | 2019-02-01 | 2019-05-31 | 中国科学院过程工程研究所 | A kind of positive electrode material precursor, and its preparation method and application |
| CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
| CN112299487A (en) * | 2019-07-30 | 2021-02-02 | 北京大学 | All-manganese or high-manganese-based lithium-rich layered cathode material with disordered cations in layer and preparation method thereof |
| CN113078298A (en) * | 2020-01-06 | 2021-07-06 | 中国科学院物理研究所 | Sodium-magnesium-iron-manganese-based layered oxide material, preparation method and application |
| CN113258060A (en) * | 2020-02-11 | 2021-08-13 | 中国科学院物理研究所 | Sodium ion battery high-nickel layered oxide material and preparation method and application thereof |
| CN113629299A (en) * | 2021-07-12 | 2021-11-09 | 河北光兴半导体技术有限公司 | Solid-state battery and preparation process thereof |
| CN113964304A (en) * | 2021-10-20 | 2022-01-21 | 吕宜媛 | Doped layered positive electrode material and preparation method thereof |
| CN114132971A (en) * | 2021-11-26 | 2022-03-04 | 西安交通大学 | Sodium ion battery positive electrode material with composite symbiotic structure, preparation method and sodium ion battery |
| CN114229918A (en) * | 2021-12-20 | 2022-03-25 | 北京化工大学 | Method for regulating phase proportion in positive electrode material of sodium-ion battery, preparation and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125069A (en) * | 2022-08-12 | 2022-09-30 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium-ion battery and application thereof |
| CN115125069B (en) * | 2022-08-12 | 2023-11-14 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium ion battery and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114784241B (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8968925B2 (en) | Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode | |
| CN103199229B (en) | Polyanion-doped lithium-enriched layered oxide anode material as well as preparation and application thereof | |
| CN103000884A (en) | Vanadium sodium phosphate composite material as well as preparation method and application thereof | |
| CN110364711A (en) | A kind of nickel cobalt manganese anode material and preparation method thereof of gradient rubidium doping | |
| CN104766971B (en) | Positive electrode, the water system battery containing positive electrode | |
| CN112968165A (en) | Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method | |
| CN113046768B (en) | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery | |
| CN111540963A (en) | Water-fused-salt-based zinc electrolyte and application thereof in secondary zinc battery | |
| CN113903884B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN114229918B (en) | Method for regulating phase proportion in positive electrode material of sodium-ion battery, preparation and application thereof | |
| WO2022205667A1 (en) | Silicon-based negative electrode material, and preparation method therefor and application thereof | |
| CN111646460A (en) | Preparation method of zinc ion battery positive electrode material | |
| US20150357653A1 (en) | Vanadium Solid-Salt Battery and Method for Producing Same | |
| CN105226269A (en) | A kind of nickel ion doped manufacturing process | |
| CN108321381A (en) | A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of Ti doping | |
| CN115498232A (en) | Electrolyte and all-vanadium redox flow battery | |
| CN114784241B (en) | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN114094089A (en) | Positive electrode lithium supplement additive, preparation thereof and application thereof in lithium supplement of positive electrode of lithium ion battery | |
| CN105810933A (en) | Preparation method for molybdenum-doped zinc-oxide-coated lithium-rich manganese-based positive electrode material | |
| CN104979557A (en) | High-rate lithium iron phosphate positive electrode material and battery electrode sheet | |
| CN110492099B (en) | Layered polyanion positive electrode material, preparation method, potassium ion battery positive electrode, potassium ion battery and application | |
| CN116169247A (en) | Prussian blue analogue coated solid-state battery positive electrode material and preparation method thereof | |
| CN109119635A (en) | battery | |
| CN101815815A (en) | Composite compound with mixed crystalline structure | |
| CN106058221A (en) | Preparation method for lithium-rich manganese-based positive electrode material coated by phosphate polyanion composite manganese salt |
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 |