CN116598462A - Layered positive electrode material of sodium ion battery and preparation method thereof - Google Patents
Layered positive electrode material of sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN116598462A CN116598462A CN202310683354.XA CN202310683354A CN116598462A CN 116598462 A CN116598462 A CN 116598462A CN 202310683354 A CN202310683354 A CN 202310683354A CN 116598462 A CN116598462 A CN 116598462A
- Authority
- CN
- China
- Prior art keywords
- sodium
- positive electrode
- ion battery
- electrode material
- layered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 60
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 89
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- 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 abstract description 50
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910013184 LiBO Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003514 Sr(OH) Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000003918 potentiometric titration Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000013078 crystal Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000011572 manganese Substances 0.000 description 15
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000012692 Fe precursor Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Abstract
The application provides a layered positive electrode material of a sodium ion battery and a preparation method thereof, wherein sodium Na is remained on the surface of the layered positive electrode material of the sodium ion battery 2 CO 3 The mass percentage of the total substances is 0.05-0.20%, and the mass percentage of the surface residual sodium NaOH is 0.04-0.16%. According to the application, M1 and M2 are used for co-doping, besides the two elements are used for respectively fluxing and improving the cycle performance, the co-doping of the two elements also has a synergistic effect, and the residual alkali on the surface of the positive electrode material can be regulated and controlled by influencing the binding energy.
Description
Technical Field
The application belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material and a preparation method thereof.
Background
Energy storage batteries have evolved from lead acid batteries to lithium ion batteries as a major key accessory for clean energy. Lithium ion batteries are widely used in the fields of electronic products, power batteries and the like as rechargeable secondary batteries, and have the highest volumetric specific energy and mass specific energy. However, as lithium ore resources continue to be mined, the cost of lithium ion batteries is gradually increased. On the other hand, the lithium ion battery still has the problems of safety, long service life, poor low-temperature performance and the like. Therefore, development of a new secondary battery that can replace a lithium ion battery is required.
The sodium ion battery is similar to the lithium ion battery in principle, when the sodium ion battery is in a charged state, sodium ions of the positive electrode are separated, migrate to the negative electrode under the action of potential and are embedded into lattices between the negative electrode layers, and when the battery is in a discharged state, the process is opposite to the process. Therefore, the capacity of the sodium ion battery is also derived from sodium ions repeatedly intercalated and deintercalated between the positive electrode and the negative electrode, and the more sodium ions intercalated into the negative electrode during charging, the higher the positive electrode charge capacity, the more sodium ions intercalated into the positive electrode during discharging, and the higher the positive electrode discharge capacity. Sodium ion batteries have attracted extensive interest in scientific research and industry as a new generation of energy storage products because of the abundance of sodium sources and low cost, and the higher safety factor of sodium ion batteries compared to lithium ion batteries. As the main improvement direction of the sodium ion battery, there are mainly layered transition metal oxides, tunnel oxides, polyanion compounds, prussian blue analogues, and the like. However, the tunnel oxide has a low sodium content and a low theoretical capacity; the polyanion compound has complex synthesis and poor conductivity; prussian blue analogues contain crystal water, are difficult to control in the material preparation process, and have low tap density, so that the energy density of the battery is affected.
Layered transition metal oxide Na 1-x MO 2 The closer the x value is to 0, the more stable the structure, and therefore the higher the sodium content, the higher the theoretical capacity. On the basis, the layered transition metal oxide is the most promising sodium ion positive electrode material at present due to the large specific capacity, high ion conductivity and feasible preparation conditions. Compared with the Na content in the P2 type layered transition metal oxide is usually less than or equal to 0.8, the Na content in the O3 type layered material is usually between 0.8 and 1.0, so that the O3 type material has higher energy density, and the preparation mode is simple and is more suitable for industrial production.
However, the O3 phase layered material is sensitive to air and water, water molecules are easily embedded into a sodium layer, sodium ions are separated, structural change is caused, residual alkali on the surface is increased, and electrochemical circulation is not facilitated, so that the residual sodium on the surface of the positive electrode material needs to be regulated and controlled, and electrochemical performance degradation caused by excessive residual sodium is avoided. In addition, the surface residual sodium can reflect whether the sodium ions contained in the material are sufficient, and if the residual sodium is too low under the same chemical formula and the preparation process, the actual sodium is not sufficiently prepared. The current methods for reducing the residual alkali on the surface are mainly surface coating and acid washing, carbon materials [ Sustainable Mater, technology, 2021, 28, e00258, electrochem, commun, 2012, 22, 85-88, J, alloys Compd, 2021, 866, 158950 ], metal oxides [ J, alloys Compd, 2021, 855, 157533, trans, non ferrous Met, soc, china 2022, 32, ACS appl, energy, mater, 2020, 3, 933-942 ], phosphates [ chem, eng, J, 2020, 382, 12269, chem, eng, J, 2020, 384, 123234 ] are all currently the main coating materials, and the application No. CN114725357A describes a method for reacting an acidic solution with residual sodium on the surface of a positive electrode material and then calcining the positive electrode material together with the coating agent, thereby reducing the electrochemical performance of the positive electrode material on the surface. These methods all have good results in terms of improving material properties, but one aspect of the uniformity and integrity of the coating is our control, and on the other hand, too thick a coating can reduce the conductivity of the electrode, which is detrimental to ion and electron transport. In addition, the added coating and acid washing steps further increase the manufacturing cost and increase the unstable factors of the steps.
Disclosure of Invention
The application aims to solve the technical problem that the electrochemical performance is not ideal due to the excessive residual sodium on the surface of a sodium ion layered anode material, overcomes the defects and the shortcomings in the background art, and provides a sodium ion battery layered anode material with low residual sodium and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the application is as follows:
sodium ion battery layered positive electrode material, wherein sodium Na is remained on surface of sodium ion battery layered positive electrode material 2 CO 3 The mass percentage of the total substances is 005% -0.20%, and the mass percentage of the surface sodium NaOH to the total substances is 0.04% -0.16%. Materials outside the range have over high alkalinity, so that the materials are easy to absorb water and wet, the viscosity is increased during homogenization, the processing performance is poor, and the subsequent capacity loss is too fast; too low alkalinity indicates that the actual sodium is insufficient or the internal defects of the material are too large, resulting in lower initial capacity or increased capacity fade.
Preferably, the chemical formula of the layered positive electrode material of the sodium ion battery is Na a Ni b Fe c Mn d Cu e M1 f M2 g O h The method comprises the steps of carrying out a first treatment on the surface of the Wherein, M1 element is one or more of Sr, nb and B, and M2 element is one or more of Zr, W, ca, mg, al, ti, P, N, mo or Y; wherein a is more than or equal to 0.9 and less than or equal to 1.1,0.2, b is more than or equal to 0.7, c is more than or equal to 0.2 and less than or equal to 0.7, d is more than or equal to 0.2 and less than or equal to 0.7,0 and less than or equal to e is more than or equal to 0.3, f is more than 0 and less than 0.05, g is more than 0 and less than 0.05,1.95, and h is more than 2.05. According to the technical scheme, the M1 element is doped in the layered positive electrode material of the sodium ion battery, and the fluxing characteristic is utilized, so that the sintering temperature of the material is reduced, and the cost is reduced; m2 element is doped, so that the structural stability of the material is improved, and the cycle life of the material is prolonged; and the co-doping of M1 and M2 has a synergistic effect, and partial transition metal elements or oxygen elements are respectively replaced to enable the transition metal layer or the oxygen layer to be in a negative valence state, so that the bonding strength of sodium ions, the transition metal layer and the oxygen atom layer is enhanced, the surface residual alkali of the positive electrode material is adjusted, and the surface residual alkali of a sample is in a better level.
More preferably, 1.03.ltoreq.a.ltoreq.1.08, and the loss of material capacity outside this range is large.
More preferably, 0.4 < f/g < 2.5; more preferably, the co-doped combination of M1 and M2 is Sr/Mg, nb/P, B/Li. The co-doping combination of the groups enables the transition metal layer or the oxygen layer to be in a negative valence state, enhances the Na+ bonding strength with a positive valence state, and reduces the residual alkali on the surface.
Preferably, the method for testing the surface sodium residue comprises the following steps: using an organic solvent as a residual alkali test solvent, adding an acid solution to perform acid-base neutralization by utilizing the solubility difference of strong alkali and weak alkali in the organic solvent, and using a potentiometric titration method to test the residual Na of a sample 2 CO 3 And NaOH content.
The calculation formula is as follows:
NaOH%=
Na 2 CO 3 %=
v1 is the volume of the acid standard solution consumed by the first equivalence point, V2 is the volume of the acid standard solution consumed by the second equivalence point (comprising the first equivalence point), V is the volume of the constant volume of the sample, and the units are mL.
Preferably, the organic solvent comprises one or more of methanol, ethanol, isopropanol, ethylene glycol, benzyl alcohol or glycerol; the acid used in the neutralization of the acid and the alkali is one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid or oxalic acid.
Under the same technical conception, the application also provides a preparation method of the layered positive electrode material of the sodium ion battery, which comprises the following steps:
(1) Mixing a salt solution containing Ni, fe and Mn or a salt solution of Ni, fe, mn, cu according to a proportion to carry out coprecipitation reaction, so as to prepare a ternary or quaternary precursor material;
(2) And mixing the precursor material, a sodium source and a compound containing M1 and M2 elements, sintering, cooling to room temperature, crushing and sieving to obtain the sodium-electricity layered anode material.
The doping substitution can be completed by adding the M1 or the M1 and the M2 elements and performing heat treatment, and the M1 element can improve the lattice energy of the material to stabilize the electrode crystal structure, so that the cycle performance and the heat stability of the material are improved, and the co-doping of the M1 element and the M2 element has a synergistic effect to further influence the bonding energy.
Preferably, the sintering schedule in the step (2) is two-step sintering, including sintering at 450-600 ℃ for 3-8 hours and at 820-1000 ℃ for 10-15 hours. And the constant-temperature sintering stage is added to pre-oxidize the precursor, so that internal defects are eliminated, anisotropy in the grain growth process is inhibited, the subsequent full melting reaction of a sodium source and the precursor is facilitated, and the residual sodium which cannot enter the crystal lattice on the surface is reduced.
Preferably, in the cooling process in the step (2), the cooling rate is controlled to be 0.3-0.7 ℃/min, so that excessive sodium residue caused by precipitation of sodium ions between layers due to excessive cooling rate is avoided, and the energy consumption is increased due to excessive cooling rate.
Preferably, the atmosphere in the step (2) is compressed air, the dew point is < -30 ℃, the humidity is less than 1%, and the rise of residual sodium caused by precipitation of interlayer sodium ions is further avoided.
The sodium source includes Na 2 CO 3 、NaHCO 3 Or NaOH; the M1 element-containing compound comprises SrCO 3 、SrO、SrSO 4 、Sr(OH) 2 ·8H 2 O、H 3 BO 3 、B 2 O 3 、Nb 2 O 5 Or (b)One or more of the following; the M2 element-containing compound comprises Li 2 TiO 3 、TiO 2 、Al 2 O 3 、Al(OH) 3 、CaO、Mg(OH) 2 、/>、MgO、H 3 PO 4 、Na 3 PO 4 、/>、Li 3 BO 3 、LiBO 2 Or Li (lithium) 2 CO 3 One or more of the following.
Compared with the prior art, the layered positive electrode material of the sodium ion battery has the beneficial effects that:
(1) According to the application, M1 and M2 are used for co-doping, besides the two elements are used for respectively fluxing and improving the cycle performance, the co-doping of the two elements also has a synergistic effect, and the residual alkali on the surface of the positive electrode material can be regulated and controlled by influencing the binding energy. When sodium Na is remained on the surface of the sodium-electricity positive electrode material 2 CO 3 Accounting for 0.05 to 0.20 percent of the total mass percent,NaOH is 0.04% -0.16%, so that poor electrochemical performance caused by too high or too low residual alkali on the surface of the material can be effectively avoided, and adverse effects on the capacity and circulation of the anode material are avoided.
(2) The application increases the presintering constant temperature stage, controls the cooling rate and uses compressed air, and prevents interlayer sodium ions from separating out by fully melting the sodium source and the precursor, thereby further reducing the surface residual sodium.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an FE-SEM image of a layered polycrystalline cathode material of a sodium ion battery of example 1;
FIG. 2 is an FE-SEM image of a layered single crystal positive electrode material of a sodium ion battery of example 2;
FIG. 3 is an FE-SEM image of a layered single crystal positive electrode material of a sodium ion battery of example 3;
fig. 4 is a charge-discharge graph of the layered polycrystalline cathode materials of the sodium ion batteries of example 1 and comparative examples 1 and 2;
fig. 5 is a graph of the capacity retention rate of a 100-turn battery of the layered polycrystalline cathode material of the sodium-ion battery of example 1 and comparative examples 1, 2;
fig. 6 is a charge-discharge curve diagram of a layered single crystal positive electrode material of a sodium ion battery of example 2 and comparative examples 3, 4, 5;
fig. 7 is a graph of the capacity retention rate of a 100-turn battery of the layered single-crystal cathode material of the sodium-ion battery of example 2 and comparative examples 3, 4, 5;
fig. 8 is a charge-discharge curve diagram of a layered single-crystal positive electrode material of a sodium ion battery of example 3 and comparative examples 6 and 7;
fig. 9 is a graph of the capacity retention rate of a 100-turn battery of the layered single-crystal cathode material for sodium ion batteries of example 3 and comparative examples 6 and 7.
Detailed Description
The present application will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the application, but the scope of the application is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
Example 1
The layered polycrystalline positive electrode material of the sodium ion battery of the embodiment has a chemical formula of Na 1.03 Ni 0.31 Fe 0.31 Mn 0.33 B 0.0 2 Li 0.02 O 2 Testing residual sodium Na 2 CO 3 The mass fraction is 0.1873%, and the NaOH content is 0.1324%. The FE-SEM of the layered positive electrode material of the sodium ion battery of this example is shown in FIG. 1.
The preparation method of the layered polycrystalline anode material of the sodium ion battery comprises the following steps:
(1) Preparing a nickel-manganese-iron precursor: according to the mole ratio of 1:1:1 preparing 1.0mol/L sulfate or nitrate solution containing Ni, mn and Fe, and precipitating agent NaOH solution and complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle in parallel, heating and stirring to perform coprecipitation reaction, performing solid-liquid separation on slurry after the reaction is completed, washing the separated solid by deionized water, and drying in an oven to obtain a nickel-iron-manganese precursor;
(2) The nickel-iron-manganese precursor and Na 2 CO 3 、LiBO 2 According to the element mole ratio of 1:1.03: and 0.02, carrying out dry mixing, heating to 450 ℃ in a compressed air atmosphere at a heating rate of 4 ℃/min after uniform mixing, and sintering for 6 hours. Then heating to 855 ℃ at a heating rate of 3 ℃/min, and sintering for 12h. Finally cooling at a cooling rate of 0.5 ℃/minCooling to room temperature, sieving to obtain Na-electric layered polycrystalline anode material with chemical formula of Na 1.03 Ni 0.31 Fe 0.31 Mn 0.33 B 0.02 Li 0.02 O 2 。
Example 2
The layered single crystal positive electrode material of the sodium ion battery of the embodiment has a chemical formula of Na 1.06 Ni 0.33 Fe 0.324 Mn 0.33 Nb 0.006 P 0.006 O 1.994 Testing residual sodium Na 2 CO 3 The mass fraction is 0.0940%, and the NaOH content is 0.1025%. The FE-SEM of the layered positive electrode material of the sodium ion battery of this example is shown in FIG. 2.
The preparation method of the layered single crystal positive electrode material of the sodium ion battery comprises the following steps:
(1) Preparing a nickel-manganese-iron precursor: according to the mole ratio of 1:1:1 preparing 1.0mol/L sulfate or nitrate solution containing Ni, mn and Fe, and precipitating agent NaOH solution and complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle in parallel, heating and stirring to perform coprecipitation reaction, performing solid-liquid separation on slurry after the reaction is completed, washing the separated solid by deionized water, and drying in an oven to obtain a nickel-iron-manganese precursor;
(2) The nickel-iron-manganese precursor and Na 2 CO 3 、Nb 2 O 5 、H 3 PO 4 According to the element mole ratio of 1:1.06:0.006:0.006, mixing uniformly, heating to 450 ℃ in a compressed air atmosphere at a heating rate of 4 ℃/min, and sintering for 6 hours. Then heating to 985 ℃ at a heating rate of 3 ℃/min, and sintering for 12 hours. Finally cooling to room temperature at a cooling rate of 0.5 ℃/min, and sieving to obtain the sodium-electricity layered single crystal anode material with a chemical formula of Na 1.06 Ni 0.33 Fe 0.324 Mn 0.33 Nb 0.006 P 0.006 O 1.9 94 。
Example 3
The layered single crystal positive electrode material of the sodium ion battery of the embodiment has a chemical formula of Na 1.05 Ni 0.217 Fe 0.247 Mn 0.40 Cu 0.13 Sr 0.003 Mg 0.003 O 2 Testing residual sodium Na 2 CO 3 The mass fraction is 0.1389%, and the NaOH content is 0.1192%. The FE-SEM of the layered positive electrode material of the sodium ion battery of this example is shown in FIG. 3.
The preparation method of the layered positive electrode material of the sodium ion battery comprises the following steps:
(1) Preparing a nickel-copper-manganese-iron precursor: preparing a sulfate or nitrate solution containing Ni, mn, fe, cu and a precipitator NaOH solution and a complexing agent NH according to the mole number 3 ·H 2 Adding the O solution into a reaction kettle in parallel, heating and stirring to perform coprecipitation reaction, performing solid-liquid separation on slurry after the reaction is completed, washing the separated solid by deionized water, and drying the separated solid by an oven to obtain a sodium-electricity nickel-iron-manganese precursor;
(2) The sodium-electricity nickel-iron-manganese precursor and Na 2 CO 3 、SrCO 3 MgO in the element mole ratio of 1:1.05:0.003:0.003, and after being mixed uniformly, heating to 450 ℃ at a heating rate of 4 ℃/min in a compressed air atmosphere, and sintering for 6 hours. Then heating to 915 ℃ at a heating rate of 3 ℃/min, and sintering for 12h. Finally cooling to room temperature at a cooling rate of 0.5 ℃/min, and sieving to obtain the sodium-electricity layered single crystal anode material with a chemical formula of Na 1.05 Ni 0.217 Fe 0.247 Mn 0.40 Cu 0.13 Sr 0.003 Mg 0.003 O 2 。
Comparative example 1
The layered polycrystalline positive electrode material of the sodium ion battery of the comparative example has a chemical formula of Na 1.03 Ni 0.27 Fe 0.31 Mn 0.33 B 0.0 6 Li 0.02 O 2 Removing nickel-iron-manganese precursor and Na 2 CO 3 、H 3 BO 3 、Li 2 CO 3 According to the element mole ratio of 1:1.03:0.06:0.02, the preparation method is identical to that of the positive electrode material of example 1, and sodium residue Na is tested 2 CO 3 The mass fraction is 0.6806%, and the NaOH content is 0.1682%.
Comparative example 2
The comparative example is Na 1.03 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The preparation method of the layered polycrystalline cathode material is the same as that of the cathode material of example 1 except that M1 and M2 substances are not added, and the sodium residue Na is tested 2 CO 3 The mass fraction is 0.6617%, and the NaOH content is 0.2174%.
Comparative example 3
The layered single crystal positive electrode material of the sodium ion battery of the embodiment has a chemical formula of Na 1.06 Ni 0.33 Fe 0.324 Mn 0.33 Nb 0.006 O 2 Removing nickel-iron-manganese precursor and Na 2 CO 3 、Nb 2 O 5 According to the element mole ratio of 1:1.06:0.006, the preparation method is the same as that of the positive electrode material of example 2, and sodium residue Na is tested 2 CO 3 The mass fraction is 0.2164%, and the NaOH content is 0.1657%.
Comparative example 4
The layered single crystal positive electrode material of the sodium ion battery of the embodiment has a chemical formula of Na 1.06 Ni 0.33 Fe 0.324 Mn 0.3 3 P 0.006 O 1.994 Removing nickel-iron-manganese precursor and Na 2 CO 3 、H 3 PO 4 According to the element mole ratio of 1:1.06:0.006, the preparation method is the same as that of the positive electrode material of example 2, and sodium residue Na is tested 2 CO 3 The mass fraction is 0.2318%, and the NaOH content is 0.1958%.
Comparative example 5
The comparative example is Na 1.02 Ni 0.33 Fe 0.324 Mn 0.33 Nb 0.006 P 0.006 O 1.994 Layered single crystal positive electrode material, sodium-removing electric nickel-iron-manganese precursor and Na 2 CO 3 、Nb 2 O 5 、H 3 PO 4 According to the element mole ratio of 1:1.02:0.006:0.006, the preparation method is the same as that of the positive electrode material of example 2, and sodium residue Na is tested 2 CO 3 The mass fraction is 0.0452 percent, and the NaOH content is 0.0341 percent.
Comparative example 6
The comparative example is Na 1.05 Ni 0.217 Fe 0.247 Mn 0.40 Cu 0.13 Sr 0.003 Mg 0.003 O 2 The preparation method of the layered single crystal positive electrode material is identical with that of the positive electrode material of example 3 except that the sintering atmosphere is natural air, and a pre-sintering platform which is used for preserving heat for 6 hours at 450 ℃ is not used in the sintering process, and the residual sodium Na is tested 2 CO 3 The mass fraction is 1.2532%, and the NaOH content is 0.6565%.
Comparative example 7
The comparative example is Na 1.05 Ni 0.217 Fe 0.247 Mn 0.40 Cu 0.13 Sr 0.003 Mg 0.003 O 2 Layered single crystal positive electrode material, the preparation method of which is consistent with that of the positive electrode material of example 3 except that the cooling rate is more than 0.7 ℃/min, and the residual sodium Na is tested 2 CO 3 The mass fraction is 0.8371%, and the NaOH content is 0.2258%.
The residual sodium test methods of examples 1 to 3 and comparative examples 1 to 7 are as follows: respectively taking 10g of samples, dissolving in 100mL of glycerol solution, stirring for 10-30 min, and then carrying out suction filtration and taking filtrate. Preparing 0.1mol/L HCl solution, placing in an automatic potentiometric titrator, titrating in an isocratic mode, recording the volume of HCl consumed during jump points, calculating the residual sodium content of the sample according to the formula, and repeating for 3 times. The test average was taken. And the anode is prepared as a metal sodium sheet, and the anode is subjected to 0.1C constant current charge and discharge twice in a voltage range of 2.0-4.2V at normal temperature, and then subjected to 100 cycles at 1C, and the test results and the residual sodium results are shown in Table 1 together.
TABLE 1
Table 1 illustrates that the addition of M1 and M2 elements to replace cations or anions in the examples can reduce the residual alkali on the surface of the material, and the reduction degree of the residual sodium on the surface can be adjusted by changing the content of the two elements. The synergy of M1 and M2 can effectively increase cycle retention without affecting capacity as compared to the comparative example. When the doping content is too high, the residual sodium is low, but the internal defects are serious, so that capacity loss is caused. When the actual sodium is not sufficiently prepared, the residual sodium is low, but the active substances are too little, so the first-round capacity is too low. The presintering section is increased, compressed air is used, the cooling rate is controlled, residual alkali can be effectively reduced, and the cycle life is prolonged. See in particular figures 4-9.
Claims (7)
1. A layered positive electrode material of a sodium ion battery is characterized in that sodium Na is remained on the surface of the layered positive electrode material of the sodium ion battery 2 CO 3 The mass percentage of the total substances is 0.05-0.20%, and the mass percentage of the surface residual sodium NaOH is 0.04-0.16%.
2. The layered positive electrode material of a sodium ion battery of claim 1, wherein the layered positive electrode material of a sodium ion battery has a chemical formula Na a Ni b Fe c Mn d Cu e M1 f M2 g O h The method comprises the steps of carrying out a first treatment on the surface of the Wherein, M1 element is one or more of Sr, nb and B, and M2 element is one or more of Zr, W, ca, mg, al, ti, P, N, mo or Y; wherein a is more than or equal to 0.9 and less than or equal to 1.1,0.2, b is more than or equal to 0.7, c is more than or equal to 0.2 and less than or equal to 0.7, d is more than or equal to 0.2 and less than or equal to 0.7,0 and less than or equal to e is more than or equal to 0.3, f is more than 0 and less than 0.05, g is more than 0 and less than 0.05,1.95, and h is more than 2.05.
3. The layered cathode material of a sodium ion battery according to claim 1, wherein the method for testing the residual sodium on the surface comprises the following steps: using an organic solvent as a residual alkali test solvent, adding an acid solution to perform acid-base neutralization by utilizing the solubility difference of strong alkali and weak alkali in the organic solvent, and using a potentiometric titration method to test the residual Na of a sample 2 CO 3 And NaOH content.
4. The layered cathode material for a sodium ion battery of claim 3, wherein the organic solvent comprises one or more of methanol, ethanol, isopropanol, ethylene glycol, benzyl alcohol, or glycerol; the acid used in the neutralization of the acid and the alkali is one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid or oxalic acid.
5. A method for preparing the layered positive electrode material of sodium ion battery as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Mixing a salt solution containing Ni, fe and Mn or a salt solution of Ni, fe, mn, cu according to a proportion to carry out coprecipitation reaction, so as to prepare a ternary or quaternary precursor material;
(2) And mixing the precursor material, a sodium source and a compound containing M1 and M2 elements, sintering, cooling to room temperature, crushing and sieving to obtain the sodium-electricity layered anode material.
6. The preparation method of claim 5, wherein the sintering schedule in the step (2) is two-step sintering, the two-step sintering comprises performing a first-stage sintering at 450-600 ℃ for 3-8 hours and a second-stage sintering at 820-1000 ℃ for 10-15 hours;
the sintering atmosphere in the step (2) is compressed air, the dew point is less than-30 ℃, and the humidity is less than 1%;
and (3) controlling the cooling rate to be 0.3-0.7 ℃/min in the cooling process in the step (2).
7. The method of claim 5, wherein the sodium source comprises Na 2 CO 3 、NaHCO 3 Or NaOH; the M1 element-containing compound comprises SrCO 3 、SrO、SrSO 4 、Sr(OH) 2 ·8H 2 O、H 3 BO 3 、B 2 O 3 、Nb 2 O 5 Or Nb (Nb) 2 O 5 ·nH 2 One or more of O; the M2 element-containing compound comprises Li 2 TiO 3 、TiO 2 、Al 2 O 3 、Al(OH) 3 、CaO、Mg(OH) 2 、、MgO、H 3 PO 4 、Na 3 PO 4 、/>、Li 3 BO 3 、LiBO 2 Or Li (lithium) 2 CO 3 One or more of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310683354.XA CN116598462A (en) | 2023-06-09 | 2023-06-09 | Layered positive electrode material of sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310683354.XA CN116598462A (en) | 2023-06-09 | 2023-06-09 | Layered positive electrode material of sodium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116598462A true CN116598462A (en) | 2023-08-15 |
Family
ID=87595616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310683354.XA Pending CN116598462A (en) | 2023-06-09 | 2023-06-09 | Layered positive electrode material of sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116598462A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116986649A (en) * | 2023-09-11 | 2023-11-03 | 湖南长远锂科新能源有限公司 | Low-residual-alkali sodium-electricity positive electrode material, preparation method thereof and sodium-ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710838A (en) * | 2020-05-25 | 2020-09-25 | 溧阳中科海钠科技有限责任公司 | Preparation method and application of modified sodium-ion battery positive electrode material |
| CN114725357A (en) * | 2022-05-06 | 2022-07-08 | 蜂巢能源科技股份有限公司 | Method for reducing residual sodium content of sodium ion cathode material |
| CN114843498A (en) * | 2022-03-30 | 2022-08-02 | 北京当升材料科技股份有限公司 | Sodium-containing oxide positive electrode material, preparation method and application thereof, positive electrode plate and application thereof |
| 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 |
| CN115148984A (en) * | 2022-09-02 | 2022-10-04 | 湖州超钠新能源科技有限公司 | O3-P2 composite phase sodium ion positive electrode material and preparation method and application thereof |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN115763717A (en) * | 2022-09-07 | 2023-03-07 | 孚能科技(赣州)股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery |
| CN116190619A (en) * | 2023-04-18 | 2023-05-30 | 溧阳中科海钠科技有限责任公司 | Layered sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
-
2023
- 2023-06-09 CN CN202310683354.XA patent/CN116598462A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710838A (en) * | 2020-05-25 | 2020-09-25 | 溧阳中科海钠科技有限责任公司 | Preparation method and application of modified sodium-ion battery positive electrode material |
| CN114843498A (en) * | 2022-03-30 | 2022-08-02 | 北京当升材料科技股份有限公司 | Sodium-containing oxide positive electrode material, preparation method and application thereof, positive electrode plate and application thereof |
| CN114725357A (en) * | 2022-05-06 | 2022-07-08 | 蜂巢能源科技股份有限公司 | Method for reducing residual sodium content of sodium ion cathode material |
| 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 |
| CN115148984A (en) * | 2022-09-02 | 2022-10-04 | 湖州超钠新能源科技有限公司 | O3-P2 composite phase sodium ion positive electrode material and preparation method and application thereof |
| CN115763717A (en) * | 2022-09-07 | 2023-03-07 | 孚能科技(赣州)股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN116190619A (en) * | 2023-04-18 | 2023-05-30 | 溧阳中科海钠科技有限责任公司 | Layered sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 朱晓辉;庄宇航;赵旸;倪明珠;徐璟;夏晖;: "钠离子电池层状正极材料研究进展", 储能科学与技术, no. 05, 5 September 2020 (2020-09-05) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116986649A (en) * | 2023-09-11 | 2023-11-03 | 湖南长远锂科新能源有限公司 | Low-residual-alkali sodium-electricity positive electrode material, preparation method thereof and sodium-ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931738B (en) | Complex-phase high-voltage cathode material and preparation method thereof | |
| CN110504432B (en) | Nickel cobalt lithium manganate composite material and preparation method thereof, lithium battery positive electrode and preparation method thereof, lithium battery and power supply device | |
| JP6016329B2 (en) | Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery and lithium ion battery | |
| CN111422925B (en) | High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile | |
| CN112103496B (en) | High-nickel ternary cathode material and preparation method thereof | |
| CN113644272B (en) | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof | |
| CN113363476B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN114497527B (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN113845152A (en) | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
| CN116613294A (en) | Sodium ion positive electrode material with low residual alkali content and preparation method thereof | |
| CN114142037A (en) | Method for preparing ultra-high nickel anode material by adopting gradient lithium supplement and prepared ultra-high nickel anode material | |
| CN112701276A (en) | Quaternary polycrystalline positive electrode material and preparation method and application thereof | |
| CN116598462A (en) | Layered positive electrode material of sodium ion battery and preparation method thereof | |
| CN115763753A (en) | Modified lithium-rich cathode material and preparation method thereof | |
| JP2024515954A (en) | High nickel positive electrode material, its preparation method and lithium ion battery | |
| CN117080412A (en) | Sodium ion battery positive electrode material, preparation method, positive electrode plate and sodium ion battery | |
| CN113620353B (en) | Strontium titanate modified nickel cobalt lithium manganate positive electrode material and lithium ion battery containing same | |
| CN114573050A (en) | Modified preparation method of ternary cathode material of lithium ion battery | |
| CN117038888A (en) | Method for carrying out structural optimization on lithium-rich positive electrode material by adopting high-valence ion doping | |
| CN116487580A (en) | Single crystal positive electrode material, preparation method thereof and lithium ion battery | |
| WO2023060992A1 (en) | Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application | |
| CN116053458A (en) | Doped NCM ternary positive electrode material, preparation method thereof, positive electrode and lithium ion battery | |
| CN115241435A (en) | Layered Na 3 M 2 XO 6 Oxide-coated modified sodium manganate cathode material and preparation method thereof | |
| CN114933335A (en) | High-nickel ternary cathode material and preparation method thereof |
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 |