CN113929069B - Manganese-rich phosphate positive electrode material and preparation method and application thereof - Google Patents
Manganese-rich phosphate positive electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113929069B CN113929069B CN202111170822.0A CN202111170822A CN113929069B CN 113929069 B CN113929069 B CN 113929069B CN 202111170822 A CN202111170822 A CN 202111170822A CN 113929069 B CN113929069 B CN 113929069B
- Authority
- CN
- China
- Prior art keywords
- sodium
- manganese
- positive electrode
- electrode material
- combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/58—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material, which is an Mn-rich phosphate positive electrode material containing V and Ti, and the chemical formula of the positive electrode material is Na 3+δ+(4‑n)x+2y Ti 1‑δ‑x‑y M n+ x V δ Mn 1+y (PO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the M n+ Comprises Li + 、K + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Al 3+ 、Cr 3+ 、Fe 3+ 、Y 3+ 、La 3+ 、Ga 3+ 、Zr 4+ 、Sn 4+ 、Nb 5+ Or W 6+ Any one or a combination of at least two of the following; x is more than or equal to 0 and less than or equal to 0.5; said 0 is<Delta is less than or equal to 0.5; n is more than or equal to 1; y is more than or equal to 0 and less than or equal to 0.5. The positive electrode material prepared by the invention can obtain higher effective specific capacity, inhibit voltage hysteresis of the manganese-rich phosphate positive electrode, inhibit the structural distortion of the manganese ion ginger Taylor and the dissolution of the manganese ion, show good dynamic performance and multiplying power performance, and further improve the electrochemical performance of the material.
Description
Technical Field
The invention relates to the field of sodium ion batteries, and relates to a novel manganese-rich phosphate anode material, and a preparation method and application thereof.
Background
In this context, advanced technologies such as clean energy (solar energy, wind energy, tidal energy, etc.) and smart grids have been unprecedented. Thus, there is also a higher demand for energy storage devices. Secondary rechargeable lithium ion battery as energy storage deviceBecause of the high conversion efficiency and energy density, extensive research has been conducted. However, the future development of lithium resources is limited by the problems of lack of lithium resources, uneven distribution and the like. With the rise of large-scale energy storage and the consideration of the characteristics of high crust abundance, low price and the like of sodium resources, the sodium ion battery becomes an important supplement for the lithium ion battery. The phosphate positive electrode material of the sodium super ion conductor has three-dimensional ion channels, so that the sodium super ion conductor is widely studied. The vanadium sodium phosphate anode has excellent rate capability and cycle capability because vanadium ions can provide a stable and flat voltage platform. However, the industrial application of the sodium vanadium phosphate is greatly limited due to the relatively expensive vanadium resources. The iron-based phosphate anode with the sodium super-ion conductor structure has the advantage of cost, but Fe 2+ /Fe 3+ The voltage platform is too low and is only about 2.5V, so that the method has no practical application value. For the manganese-based phosphate anode material which is also green and low in cost, such as vanadium manganese sodium phosphate, although two reaction pairs exist, the use amount of vanadium is still high, so that the cost of the material is still high, and industrialization is not easy to realize; for the manganese titanium phosphate material without vanadium, the price is low, and positive tetravalent titanium ions can activate Mn 2+ /Mn 3+ And Mn of 3+ /Mn 4+ Two reaction pairs with voltage platforms of 3.6V and 4.1V, respectively, even higher than V 3+ /V 4+ However, the mutual occupation of Na and Mn in the material is serious, so that the material is seriously attenuated in the sodium deintercalation process, and the material has no practical application value.
In manganese-based phosphates, because manganese ions and sodium ions have similar radiuses, manganese ions in a crystal structure are easy to occupy active sites (Na 1 sites) of sodium, and a sodium-manganese mixed discharge phenomenon is generated, so that the capacity of the material cannot be effectively exerted. During charging, divalent manganese ions oxidize to form smaller trivalent manganese ions (or tetravalent manganese ions), which migrate to a thermodynamically stable state. The migration process of the manganese ions causes serious voltage hysteresis of a charge-discharge curve, which not only reduces the output voltage of the material, but also influences the capacity release of the material in an effective voltage window. And Mn of 3+ Jahn-Teller effect and Mn of (C) 2+ Is in the presence ofDissolution in the organic electrolyte reduces the structural stability of the material and deteriorates the material dynamics. Therefore, the novel low-price Mn-rich phosphate anode is urgently developed, the defect of the above Mn-rich phosphate structure is overcome, and better multiplying power performance and cycle performance are obtained, which has important significance for future industrial application of the Mn-rich phosphate anode.
CN106981641a discloses a preparation method of carbon-coated titanium manganese sodium phosphate positive electrode material, which uses organic compound as reducer and carbon source, mixing and ball milling phosphorus source, manganese source, sodium source and titanium source, and obtaining carbon-coated titanium manganese sodium phosphate positive electrode material after high temperature sintering. Although the overall conductivity of the cathode material can be improved by introducing carbon coating, the problems of mixed arrangement of sodium and manganese, ginger Taylor effect of trivalent manganese ions, dissolution of manganese ions and the like in a titanium-manganese-sodium phosphate structure are still not solved effectively, and the titanium-manganese-sodium phosphate cathode material has lower discharge specific capacity and poorer circularity, and is difficult to realize industrial-scale mass production.
CN111092220a discloses an M element bulk phase doped modified tunnel type sodium ion battery manganese-based positive electrode material and a preparation method thereof, wherein a precursor is prepared by solid phase ball milling and a high-temperature solid phase sintering reaction is carried out to prepare the M element bulk phase doped tunnel type sodium ion battery manganese-based material with a rod-shaped structure. The M element body is doped to effectively improve the electron conductivity of the electrode material, improve the structural stability of the material and be beneficial to improving the multiplying power performance and the cycle stability of the material. Wherein M element comprises Al 3+ 、Co 3+ 、Ni 2+ 、Mg 2+ And Fe (Fe) 3+ Any one or a combination of at least two of these. Although the M element bulk doping improves the conductivity of the material, it has limitations on the improvement of the conductivity of the cathode material, and also on the improvement of the cycle performance and the rate performance of the material.
CN112563484A discloses a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery, wherein the chemical formula of the sodium ion battery positive electrode material is Na x Ni y M 1-y O 2 Wherein 0.5<x<1，0.1<y<0.5, M is selected from Mn, fe, co, V, cu,At least one of Cr and Ti; the positive electrode material of the sodium ion battery is of a similar spherical particle, and has a layered structure. Although the cycle performance of the battery cathode material is improved, the improvement of the conductivity of the battery is not beneficial.
How to improve the electrochemical performance of sodium ion batteries is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a Mn-rich phosphate positive electrode material containing V and Ti, which can obtain more effective specific capacity, inhibit voltage hysteresis of the Mn-rich phosphate positive electrode, show good dynamic performance and rate capability, inhibit the structural distortion of a manganese ion ginger Taylor and the dissolution of manganese ions, and further improve the electrochemical performance of the material.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
one of the purposes of the present invention is to provide a positive electrode material which is a Mn-rich phosphate positive electrode material containing V and Ti, and has a chemical formula of Na 3+δ+(4-n)x+2y Ti 1-δ-x-y M n+ x V δ Mn 1+y (PO 4 ) 3 。
Wherein the M n+ Comprises Li + 、K + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Al 3+ 、Cr 3+ 、Fe 3+ 、Y 3+ 、La 3+ 、Ga 3+ 、Zr 4+ 、Sn 4+ 、Nb 5+ Or W 6+ Any one or a combination of at least two, typical but non-limiting examples of which are: li (Li) + And K + Combinations of (K) + And Mg (magnesium) 2+ Is a combination of (1) and (2) 2+ And Ca 2+ Combination of (2), ca 2+ And Zn 2+ Is a combination of (C), co 2+ And Ni 2+ Is combined with Cu 2+ And Al 3+ Is a combination of (C), cr 3+ And Y 3+ And La (La) 3+ Combinations of (1), sr 2+ And Fe (Fe) 3+ And Sn (Sn) 4+ Is a combination of Ga 3+ And Zr (Zr) 4+ Or Nb of (B) 5+ And W is 6+ Combinations of (a) and the like.
The value of 0.ltoreq.x.ltoreq.0.5, wherein the value of x may be 0, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The value of 0< delta is less than or equal to 0.5, wherein the value of delta can be 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The value of n is equal to or greater than 1, wherein the value of n can be 1, 2, 3, 4, 5, 6 or 7, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The value of y is 0.ltoreq.y.ltoreq.0.5, wherein the value of y may be 0, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Compared with the prior art, the Mn-rich phosphate positive electrode material has the advantages that more effective specific capacity can be obtained due to doping of trivalent vanadium ions, and more sodium content can reduce sodium-manganese mixed discharge degree, so that voltage hysteresis of the Mn-rich phosphate positive electrode is inhibited; v (V) 3+ And Ti is 4+ Mn and 2+ has good solid solubility and synergistic effect, exhibits good dynamic performance and rate performance; while other Mn in the material + The ions can inhibit the distortion of the Taylor structure of the manganese ions and the dissolution of the manganese ions, and further improve the electrochemical performance of the material.
In the invention, V 3+ And Ti is 4+ Mn and 2+ has good solid solubility, and uses a small amount of active V for reducing the cost of raw materials 3+ With Ti 4+ And Mn of 2+ Novel Mn-rich phosphates are formed. By adjusting Mn + The values of delta, x and y introduce more sodium ions to occupy lattice sites, so that the sodium-manganese miscibility is reduced, and trivalent or tetravalent manganese ions are reduced in the electrochemical reaction processThereby inhibiting voltage hysteresis of the material. Due to V 3+ And Ti is 4+ Mn and 2+ has good solid solubility, is favorable for forming a pure phase, has a synergistic effect in the electrochemical reaction process, and shows good dynamics performance and multiplying power performance. Mn introduced into typical stabilization + The ions can obtain a more stable frame structure, inhibit the distortion of the Taylor structure of the manganese ions and the dissolution of the manganese ions, and improve the circulation stability of the material.
Another object of the present invention is to provide a method for preparing the positive electrode material according to the first aspect, the method comprising:
and mixing the raw materials of the positive electrode material with a solvent to obtain a precursor, drying the precursor, and sintering to obtain the positive electrode material.
The method for synthesizing the cathode material in the invention comprises any one of a solid phase method, a spray drying method and a sol-gel method.
As a preferable technical scheme of the invention, the raw materials comprise a sodium source, a manganese source, a titanium source, a vanadium source, a phosphorus source and a metal ion source.
As a preferred embodiment of the present invention, the sodium source comprises any one or a combination of at least two of sodium bicarbonate, sodium carbonate, sodium acetate, sodium nitrate, sodium hydroxide or sodium oxalate, and typical but non-limiting examples of such combinations are: a combination of sodium bicarbonate and sodium carbonate, a combination of sodium carbonate and sodium acetate, a combination of sodium acetate and sodium nitrate, a combination of sodium nitrate and sodium hydroxide, or a combination of sodium hydroxide and sodium oxalate, and the like.
Preferably, the manganese source comprises any one or a combination of at least two of manganese acetate, manganese nitrate, manganese acetylacetonate, manganese oxalate, manganese carbonate, manganese monoxide, manganese dioxide, manganese trioxide, manganese tetraoxide, manganous anhydride, or homomanganic anhydride, typical but non-limiting examples of such combinations being: a combination of manganese acetate and manganese nitrate, a combination of manganese acetylacetonate and manganese oxalate, a combination of manganese oxalate and manganese carbonate, a combination of manganese monoxide and manganese dioxide, a combination of manganese sesquioxide and manganese tetraoxide, a combination of manganese tetraoxide and manganous anhydride, a combination of manganous anhydride and manganese anhydride, or a combination of manganic anhydride and homomanganese anhydride, and the like.
Preferably, the titanium source comprises any one or a combination of at least two of titanium dioxide, titanium oxide, sodium titanate, titanium acetylacetonate, titanyl acetylacetonate, or tetrabutyl titanate, typical but non-limiting examples of such combinations being: a combination of titanium oxide and titanium oxide, a combination of titanium oxide and sodium titanate, a combination of sodium titanate and titanium acetylacetonate, a combination of titanium acetylacetonate and titanium acetylacetonate, or a combination of titanium acetylacetonate and tetrabutyl titanate, and the like.
Preferably, the vanadium source includes any one or a combination of at least two of various types of vanadium pentoxide, vanadium tetraoxide, vanadium trioxide, vanadium oxide, sodium ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, or vanadium acetylacetonate, typical but non-limiting examples of such combinations being: a combination of vanadium pentoxide and vanadium tetraoxide, a combination of vanadium tetraoxide and vanadium trioxide, a combination of vanadium trioxide and vanadium oxide, a combination of vanadium oxide and sodium ammonium metavanadate, a combination of sodium ammonium metavanadate and ammonium vanadate, a combination of ammonium vanadate and vanadyl acetylacetonate, or a combination of vanadyl acetylacetonate and vanadyl acetylacetonate, and the like.
Preferably, the phosphorus source comprises any one or a combination of at least two of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate, or ammonium sodium phosphate, typical but non-limiting examples of such combinations being: a combination of phosphoric acid and monoammonium sodium phosphate, a combination of monoammonium sodium phosphate and monoammonium phosphate, a combination of monoammonium phosphate and diammonium sodium phosphate, a combination of diammonium sodium phosphate and diammonium phosphate, or a combination of ammonium phosphate and ammonium sodium phosphate, and the like.
Preferably, the metal ion source comprises Li + 、K + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Al 3+ 、Cr 3 + 、Fe 3+ 、Y 3+ 、La 3+ 、Ga 3+ 、Zr 4+ 、Sn 4+ 、Nb 5+ Or W 6+ Any one or a combination of at least two of the corresponding acids, bases, sodium salts or ammonium salts, typical but non-limiting examples of which are: li (Li) + Corresponding base and K + Combinations of corresponding acids, K + Corresponding acids and Mg 2+ Combinations of corresponding bases, mg 2+ Corresponding sodium salt and Ca 2+ Combinations of corresponding ammonium salts, ca 2+ Corresponding acids and Zn 2+ Combinations of corresponding bases, co 2+ Corresponding sodium salt and Ni 2+ Combinations of corresponding bases, cu 2+ Corresponding ammonium salts and Al 3+ Combinations of corresponding acids, cr 3+ Corresponding base and Y 3+ Corresponding base and La 3+ Combinations of corresponding bases, ga 3+ Corresponding acids and Zr 4+ Combinations of corresponding bases or Nb 5+ Corresponding sodium salt and W 6+ A combination of corresponding acids, and the like.
As a preferred embodiment of the present invention, the raw material further includes a carbon source.
Preferably, the carbon source comprises any one or a combination of at least two of sodium citrate, citric acid, sodium oleate, oleic acid, polyvinylpyrrolidone, polyethylene glycol, glucose, ascorbic acid, sucrose, dopamine hydrochloride, starch, graphene oxide, reduced graphene, carbon nanotubes or ketjen black, typical but non-limiting examples of which are: a combination of sodium citrate and citric acid, a combination of citric acid and sodium oleate, a combination of sodium oleate and oleic acid, a combination of oleic acid and polyvinylpyrrolidone, a combination of polyvinylpyrrolidone and polyethylene glycol, a combination of polyethylene glycol and glucose, a combination of ascorbic acid and sucrose, a combination of dopamine hydrochloride and starch, a combination of graphene oxide and reduced graphene or a combination of carbon nanotubes and ketjen black, and the like.
Preferably, the molar ratio of the carbon source to the metal ion source is 0 to 10:1, wherein the molar ratio may be 0, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but is not limited to the recited values, other non-recited values within the range are equally applicable, and more preferably 0 to 3:1.
As a preferred embodiment of the present invention, the solvent comprises any one or a combination of at least two of deionized water, ethanol or acetone, typical but non-limiting examples of which are: a combination of deionized water and ethanol, a combination of deionized water and acetone, or a combination of ethanol and acetone, and the like.
In a preferred embodiment of the present invention, the drying is followed by a polishing treatment.
Preferably, the drying temperature is 60 to 150 ℃, the temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, or the like, but not limited to the recited values, other non-recited values within the range of values are equally applicable, more preferably 90 to 120 ℃;
preferably, the time of the grinding treatment is 1min to 48h, wherein the time can be 1min, 5min, 10min, 20min, 30min, 40min, 50min, 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. More preferably 30 minutes to 2 hours.
As a preferred embodiment of the present invention, the atmosphere for sintering includes an inert atmosphere and/or a reducing atmosphere.
Preferably, the reducing atmosphere comprises carbon monoxide and/or hydrogen.
Preferably, the inert atmosphere comprises argon and/or nitrogen.
In a preferred embodiment of the present invention, the sintering temperature is 500 to 900 ℃, wherein the temperature may be 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the sintering time is 2 to 20 hours, wherein the time may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
It is a further object of the present invention to provide a positive electrode material for use in a sodium ion battery.
The sodium ion battery is used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distribution power stations, backup power sources or communication base stations.
Compared with the prior art, the invention has the following beneficial effects:
(1) The Mn-rich phosphate positive electrode material containing V and Ti prepared by the method has the advantages of greatly reducing the cost due to small V consumption.
(2) The Mn-rich phosphate positive electrode material containing V and Ti, prepared by the invention, has good electrochemical performance, and is subjected to charge-discharge test at 0.1C, the gram specific capacity of the initial discharge reaches more than 110mAh/g, and the medium voltage of the discharge reaches more than 3.5V; more than 80mAh/g can be obtained at 10C; the capacity retention rate is more than 90% after 1000 weeks of 2C lower circulation.
Drawings
FIG. 1 is an XRD pattern of a Mn-rich phosphate positive electrode material containing V and Ti prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of a Mn-rich phosphate positive electrode material containing V and Ti prepared in example 1 of the present invention.
Fig. 3 is a graph showing the charge-discharge rate of the Mn-rich phosphate cathode material containing V and Ti prepared in example 1 of the present invention.
FIG. 4 is a graph showing the cycle performance at 2C of the Mn-rich phosphate cathode material containing V and Ti prepared in example 1 of the present invention.
FIG. 5 is a charge-discharge curve of the phosphate positive electrode prepared in example 1-2 and comparative example 1-2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides a method for preparing a Mn-rich phosphate cathode material containing V and Ti:
the composition ratio is 1:0.80:0.15:0.05:3.25:3, adding manganese acetate, titanium dioxide, ammonium metavanadate, magnesium acetate, sodium acetate and phosphoric acid into an ethanol solution containing citric acid, wherein the mass ratio of carbon to transition metal is 1.5:1. the mixed solution was then placed in a water bath with magnetic stirring at 70 degrees celsius until the ethanol was completely evaporated. Drying the obtained precursor at 100 ℃, grinding to powder state, and sintering in a tubular furnace in argon atmosphere at 700 ℃ for 10 hours to obtain Na 3.25 Ti 0.8 V 0.15 Mg 0.05 Mn(PO 4 ) 3 @ C positive electrode material.
Structural analysis is performed on the positive electrode material in the embodiment, XRD analysis is performed on the Mn-rich phosphate positive electrode material prepared in the embodiment by using an X-ray instrument, and a test result is shown in fig. 1, and it can be seen from the graph that the material has good crystallinity and higher phase purity.
The surface morphology analysis was performed on the phosphate positive electrode prepared in this example using a scanning electron microscope, and the test result is shown in fig. 2, where it can be seen that the prepared material is formed by stacking irregular primary particles. The agglomeration phenomenon is caused by embedding particles into a carbon layer and presenting a cross-linked state.
The phosphate positive electrode prepared by the embodiment is assembled into 2032 type testable button cell, and the multiplying power charge-discharge curve is shown in figure 3. The cycle performance at 2C is shown in fig. 4.
Example 2
The present example provides a method for preparing a Mn-rich phosphate cathode material containing V and Ti:
the composition ratio is 1.2:0.65:0.075:0.025:3.55:3, adding manganese carbonate, titanium dioxide, vanadium trioxide, aluminum oxide, sodium hydroxide, ammonium dihydrogen phosphate and oleic acid into an aqueous solution, wherein the mass ratio of carbon to transition metal is 3:1. the mixture was then placed in a ball mill and mixed well. Drying the obtained precursor at 110deg.C, grinding to powder state, and placingSintering for 20 hours at 750 ℃ in a tube furnace in argon atmosphere to obtain Na 3.55 Ti 0.65 V 0.10 Al 0.05 Mn 1.2 (PO 4 ) 3 @ C positive electrode material.
Example 3
The present example provides a method for preparing a Mn-rich phosphate cathode material containing V and Ti:
the composition ratio is 1:0.74:0.25:0.01:3.19:3, adding manganese acetate, tetrabutyl titanate, ammonium metavanadate, ammonium tungstate, sodium acetate and phosphoric acid into an acetone solution containing ascorbic acid, wherein the mass ratio of carbon to transition metal is 1:1. the mixed solution was then placed in a water bath with magnetic stirring at 80 degrees celsius until the acetone was completely evaporated. Drying the obtained precursor at 110 ℃, grinding to powder state, and sintering in a tube furnace in argon atmosphere at 650 ℃ for 12 hours to obtain Na 3.19 Ti 0.74 V 0.25 W 0.01 Mn(PO 4 ) 3 @ C positive electrode material.
Example 4
The present example provides a method for preparing a Mn-rich phosphate cathode material containing V and Ti:
the composition ratio was 1.15:0.7:0.05:0.05:1.775:3, adding manganese carbonate, titanium dioxide, vanadium trioxide, zirconium dioxide, sodium carbonate, ammonium dihydrogen phosphate and glucose into an aqueous solution, wherein the mass ratio of carbon to transition metal is 1.25:1. the mixture was then placed in a ball mill and mixed well. Drying the obtained precursor at 120 ℃, grinding to a powder state, and sintering in a tube furnace in argon atmosphere at 800 ℃ for 10 hours to obtain Na 3.4 Ti 0.7 V 0.10 Zr 0.05 Mn 1.15 (PO 4 ) 3 @ C positive electrode material.
Example 5
The present example provides a method for preparing a Mn-rich phosphate cathode material containing V and Ti:
the composition ratio is 1:0.75:0.25:3.25:3, manganese acetate, tetrabutyl titanate, vanadium acetylacetonate, sodium acetate andphosphoric acid was added to the ethanol solution, wherein the mass ratio of carbon to transition metal was 1.25:1. the mixture was then placed in a ball mill and mixed well. Drying the obtained precursor at 120 ℃, grinding to a powder state, and sintering in a tube furnace in argon atmosphere at 800 ℃ for 10 hours to obtain Na 3.4 Ti 0.7 V 0.10 Zr 0.05 Mn 1.15 (PO 4 ) 3 @ C positive electrode material.
Example 6
The composition ratio of this example is 1:0.80:0.15:0.05:3.25:3, adding manganese acetate, titanium dioxide, ammonium metavanadate, magnesium acetate, sodium acetate and phosphoric acid into an ethanol solution containing citric acid, wherein the mass ratio of carbon to transition metal is 1.5:1, replaced by composition ratio 1:0.80:0.15:0.05:3.25:3, adding manganese acetate, titanium dioxide, ammonium metavanadate, magnesium acetate, sodium acetate and phosphoric acid to an ethanol solution containing more citric acid so that the mass ratio of carbon and transition metal is 10:1, the other conditions were the same as in example 1.
Example 7
The composition ratio of this example is 1:0.80:0.15:0.05:3.25:3, adding manganese acetate, titanium dioxide, ammonium metavanadate, magnesium acetate, sodium acetate and phosphoric acid into an ethanol solution containing citric acid, wherein the mass ratio of carbon to transition metal is 1.5:1 is replaced by the composition ratio 1:0.80:0.15:0.05:3.25:3, manganese acetate, titanium dioxide, ammonium metavanadate, magnesium acetate, sodium acetate and phosphoric acid were added to the ethanol solution, wherein the mass ratio of carbon to transition metal was 0, and the other conditions were the same as in example 1.
Comparative example 1
The comparative example provides a method for preparing a phosphate positive electrode material containing only Ti and Mn:
the preparation method comprises the following steps:
the composition ratio is 1:1:3:3, adding manganese acetate, tetrabutyl titanate, sodium acetate and phosphoric acid into an ethanol solution containing citric acid, wherein the mass ratio of carbon to transition metal is 1.5:1. then the mixed solution is placed in a water bath kettle to be magnetically stirred at 80 DEG CStirring until ethanol is evaporated completely. Drying the obtained precursor at 100 ℃, grinding to powder state, and sintering in a tubular furnace in argon atmosphere at 700 ℃ for 10 hours to obtain Na 3 TiMn(PO 4 ) 3 @ C positive electrode material.
Comparative example 2
The comparative example provides a method for preparing a phosphate positive electrode material which only contains Ti and Mn and has more Mn content:
the composition ratio is 1.2:0.8:1.5:3, adding manganese carbonate, titanium dioxide, sodium carbonate, ammonium dihydrogen phosphate and glucose into an aqueous solution, wherein the mass ratio of carbon to transition metal is 2:1. the mixture was then placed in a ball mill and mixed well. Drying the obtained precursor at 120 ℃, grinding to a powder state, and sintering in a tube furnace in argon atmosphere at 800 ℃ for 15 hours to obtain Na 3.4 Ti 0.8 Mn 1.2 (PO 4 ) 3 @ C positive electrode material.
Comparative example 3
The comparative example provides a method for preparing a phosphate positive electrode material containing only V and Mn:
the composition ratio is 1.2:0.8:1.5:3, adding manganese carbonate, vanadium trioxide, sodium carbonate, ammonium dihydrogen phosphate and glucose into an aqueous solution, wherein the mass ratio of carbon to transition metal is 2:1. the mixture was then placed in a ball mill and mixed well. Drying the obtained precursor at 120 ℃, grinding to a powder state, and sintering in a tube furnace in argon atmosphere at 800 ℃ for 15 hours to obtain Na 3.4 Ti 0.8 Mn 1.2 (PO 4 ) 3 @ C positive electrode material.
Electrochemical performance analysis was performed on the positive electrode materials prepared in examples 1 to 5 and comparative examples 1 to 3,
wherein, the electrochemical performance analysis is as follows:
1. battery preparation
(1) Preparation of a battery positive plate: and grinding and uniformly mixing the prepared phosphate anode material, ketjen black and polytetrafluoroethylene binder according to the mass ratio of 7:2:1, and then fully rolling by a pair roller to form a film with uniform thickness. And (3) drying the positive electrode film in a vacuum drying oven at 120 ℃ for 5 hours, cutting the obtained positive electrode film into square pole pieces with the side length of about 6mm, accurately weighing the mass of the square pole pieces, and calculating the mass of active substances in the positive electrode pieces according to the composition of a formula.
(2) And (3) battery assembly:
the square positive electrode plate, the diaphragm with the diameter of 16mm, the sodium plate with the diameter of 15mm, the elastic sheet, the gasket and the like are assembled into a 2032 type testable button cell in a glove box (the oxygen content is less than 0.01ppm and the water content is less than 0.01 ppm).
2. Electrochemical performance testing method:
the assembled batteries were subjected to charge and discharge tests at various rates using the marchand blue electric high performance battery test system, and the results are shown in table 1. The charge and discharge curves of the phosphate positive electrodes prepared in example 1, example 2, comparative example 1, and comparative example 2 are shown in fig. 5.
TABLE 1
As can be seen by comparing examples 1-5 and comparative examples 1-3 above, the Ti element activates both voltage plateaus associated with the manganese-rich phosphate positive electrode and manganese; the introduction of V can obtain more effective specific capacity, and simultaneously inhibit the voltage hysteresis of the manganese-rich phosphate anode, and the V, ti and Mn three elements have better solid solution property and synergistic effect, and show good dynamic performance and multiplying power performance. And stable metal ions Mn+ are introduced, so that the structural distortion of the Taylor structure of the manganese ions and the dissolution of the manganese ions can be effectively inhibited, and the electrochemical performance of the material is further improved. As can be seen from comparing example 1 with example 7, the absence of carbon coating correspondingly deteriorates electrochemical performance due to poor electron conductivity; as can be seen from comparing example 1 with example 6, excessive carbon coating increases the interface resistance of the positive electrode material, and has more side reactions, which are detrimental to the electrochemical performance of the material.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (17)
1. A positive electrode material is characterized in that the positive electrode material is an Mn-rich phosphate positive electrode material containing V and Ti, and the chemical formula of the positive electrode material is Na 3+δ+(4-n)x+2y Ti 1-δ-x-y M n+ x V δ Mn 1+y (PO 4 ) 3 ；
Wherein the M n+ Comprises Mg 2+ 、Ca 2+ 、Sr 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Al 3+ 、Cr 3+ 、Fe 3+ 、Y 3+ 、La 3+ 、Ga 3+ 、Zr 4 + 、Sn 4+ 、Nb 5+ Or W 6+ Any one or a combination of at least two of the following;
x is more than 0 and less than or equal to 0.05;
the delta is more than 0 and less than or equal to 0.25;
n is more than or equal to 2;
the y is more than 0 and less than 0.15.
2. A method of producing the positive electrode material according to claim 1, characterized in that the method comprises:
mixing raw materials of a positive electrode material with a solvent to obtain a precursor, drying the precursor, and sintering to obtain the positive electrode material, wherein the drying is followed by grinding treatment, the sintering atmosphere comprises an inert atmosphere and/or a reducing atmosphere, the sintering temperature is 500-900 ℃, and the sintering time is 2-20 hours;
the raw materials comprise a sodium source, a manganese source, a titanium source, a vanadium source,A phosphorus source and a metal ion source comprising Mg 2+ 、Ca 2+ 、Sr 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Al 3+ 、Cr 3+ 、Fe 3+ 、Y 3+ 、La 3+ 、Ga 3+ 、Zr 4+ 、Sn 4+ 、Nb 5+ Or W 6+ Any one or a combination of at least two of corresponding acids, bases, sodium salts or ammonium salts;
the raw material further comprises a carbon source, and the molar ratio of the carbon source to the metal ion source is 0-10:1.
3. The method of claim 2, wherein the sodium source comprises any one or a combination of at least two of sodium bicarbonate, sodium carbonate, sodium acetate, sodium nitrate, sodium hydroxide, or sodium oxalate.
4. The method of claim 2, wherein the manganese source comprises any one or a combination of at least two of manganese acetate, manganese nitrate, manganese acetylacetonate, manganese oxalate, manganese carbonate, manganese monoxide, manganese dioxide, manganese sesquioxide, manganomanganic anhydride, manganese anhydride, or high manganese anhydride.
5. The method of claim 2, wherein the titanium source comprises any one or a combination of at least two of titanium dioxide, titanium sesquioxide, sodium titanate, titanium acetylacetonate, or tetrabutyl titanate.
6. The method according to claim 2, wherein the vanadium source comprises any one or a combination of at least two of various types of vanadium pentoxide, vanadium tetraoxide, vanadium trioxide, vanadium oxide, sodium ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, or vanadium acetylacetonate.
7. The method of claim 2, wherein the phosphorus source comprises any one or a combination of at least two of phosphoric acid, sodium monoammonium phosphate, sodium diammonium phosphate, ammonium phosphate, or sodium ammonium phosphate.
8. The method of claim 2, wherein the carbon source comprises any one or a combination of at least two of sodium citrate, citric acid, sodium oleate, oleic acid, polyvinylpyrrolidone, polyethylene glycol, glucose, ascorbic acid, sucrose, dopamine hydrochloride, starch, graphene oxide, reduced graphene, carbon nanotubes, or ketjen black.
9. The method according to claim 2, wherein the molar ratio of the carbon source to the metal ion source is 0 to 3:1.
10. The method of claim 2, wherein the solvent comprises any one or a combination of at least two of deionized water, ethanol, or acetone.
11. The method according to claim 2, wherein the drying temperature is 60-150 ℃.
12. The method according to claim 11, wherein the drying temperature is 90-120 ℃.
13. The method according to claim 2, wherein the time of the grinding treatment is 1min to 48 hours.
14. The method according to claim 13, wherein the time of the grinding treatment is 30min to 2h.
15. The method of claim 2, wherein the reducing atmosphere comprises carbon monoxide and/or hydrogen.
16. The method of claim 2, wherein the inert atmosphere comprises argon and/or nitrogen.
17. Use of the positive electrode material according to claim 1, wherein the positive electrode material is applied to a sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111170822.0A CN113929069B (en) | 2021-10-08 | 2021-10-08 | Manganese-rich phosphate positive electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111170822.0A CN113929069B (en) | 2021-10-08 | 2021-10-08 | Manganese-rich phosphate positive electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929069A CN113929069A (en) | 2022-01-14 |
| CN113929069B true CN113929069B (en) | 2023-09-22 |
Family
ID=79278190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111170822.0A Active CN113929069B (en) | 2021-10-08 | 2021-10-08 | Manganese-rich phosphate positive electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929069B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115084502A (en) * | 2022-05-13 | 2022-09-20 | 福州大学 | NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof |
| CN115207347A (en) * | 2022-06-27 | 2022-10-18 | 武汉工程大学 | Titanium-doped sodium vanadium manganese phosphate sodium ion battery positive electrode material and preparation method thereof |
| CN115636402B (en) * | 2022-10-28 | 2024-04-16 | 深圳市德方纳米科技股份有限公司 | Lithium iron manganese phosphate material and preparation method and application thereof |
| CN116081591B (en) * | 2023-02-23 | 2024-05-14 | 武汉工程大学 | Preparation method of negative electrode material of sodium ion battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883735A (en) * | 2007-10-01 | 2010-11-10 | 巴斯夫欧洲公司 | Process for the preparation of crystalline lithium-, vanadium- and phosphate-comprising materials |
| CN102569797A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite cathode material, its preparation method and application thereof |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN106981641A (en) * | 2017-05-11 | 2017-07-25 | 中南大学 | A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery |
| CN107425190A (en) * | 2017-09-01 | 2017-12-01 | 北京科技大学 | A kind of vanadium phosphate sodium combination electrode material and its preparation method and application |
| CN111244446A (en) * | 2020-01-17 | 2020-06-05 | 河北九丛科技有限公司 | Method for synthesizing high-voltage phosphate lithium ion battery anode material |
| CN112421040A (en) * | 2020-11-16 | 2021-02-26 | 中国科学院过程工程研究所 | Phosphate anode material and preparation method and application thereof |
| CN112786857A (en) * | 2021-01-19 | 2021-05-11 | 华南师范大学 | Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof |
| CN113353985A (en) * | 2021-05-25 | 2021-09-07 | 北京大学深圳研究生院 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode and lithium ion battery |
| CN113363483A (en) * | 2021-04-27 | 2021-09-07 | 北京当升材料科技股份有限公司 | Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery |
| CN113422043A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院过程工程研究所 | Modified titanium manganese sodium phosphate cathode material and preparation method and application thereof |
-
2021
- 2021-10-08 CN CN202111170822.0A patent/CN113929069B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883735A (en) * | 2007-10-01 | 2010-11-10 | 巴斯夫欧洲公司 | Process for the preparation of crystalline lithium-, vanadium- and phosphate-comprising materials |
| CN102569797A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite cathode material, its preparation method and application thereof |
| WO2013107186A1 (en) * | 2012-01-20 | 2013-07-25 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite anode material, preparation method and use thereof |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN106981641A (en) * | 2017-05-11 | 2017-07-25 | 中南大学 | A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery |
| CN107425190A (en) * | 2017-09-01 | 2017-12-01 | 北京科技大学 | A kind of vanadium phosphate sodium combination electrode material and its preparation method and application |
| CN111244446A (en) * | 2020-01-17 | 2020-06-05 | 河北九丛科技有限公司 | Method for synthesizing high-voltage phosphate lithium ion battery anode material |
| CN112421040A (en) * | 2020-11-16 | 2021-02-26 | 中国科学院过程工程研究所 | Phosphate anode material and preparation method and application thereof |
| CN112786857A (en) * | 2021-01-19 | 2021-05-11 | 华南师范大学 | Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof |
| CN113363483A (en) * | 2021-04-27 | 2021-09-07 | 北京当升材料科技股份有限公司 | Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery |
| CN113353985A (en) * | 2021-05-25 | 2021-09-07 | 北京大学深圳研究生院 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode and lithium ion battery |
| CN113422043A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院过程工程研究所 | Modified titanium manganese sodium phosphate cathode material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Encapsulation of Na4MnV(PO4)3 in robust dual-carbon framework rendering high-energy, durable sodium storage;CongcongCai et al.;《JOURNAL OF PHYSICS-ENERGY》;20200226;第2卷(第2期);第1-7页 * |
| NaxMV(PO4)(3) (M = Mn, Fe, Ni) Structure and Properties for Sodium Extraction;Zhou, WD et al.;《NANO LETTERS》;20161110;第16卷(第12期);第7836-7841页 * |
| Zn2+掺杂对Na0.67Ni0.33Mn0.67O2的影响;陈森等;《第31届全国化学与物理电源学术年会论文集》;20151031;第160页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929069A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113929069B (en) | Manganese-rich phosphate positive electrode material and preparation method and application thereof | |
| CN111900344B (en) | Preparation method of carbon-coated lithium manganese iron phosphate cathode material | |
| CN113422043B (en) | Modified titanium manganese sodium phosphate cathode material and preparation method and application thereof | |
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CA2741406C (en) | Multi-component-system lithium phosphate compound particles having an olivine structure, manufacturing method thereof and lithium secondary battery employing the lithium phosphate compound particles as a positive electrode material | |
| CN109301174B (en) | Positive electrode material, method for producing same, and lithium secondary battery | |
| CN112421040A (en) | Phosphate anode material and preparation method and application thereof | |
| CN107845801B (en) | Synergistically modified lithium cobalt fluorophosphate cathode material and preparation method thereof | |
| CN111082059A (en) | V-doped P2 type sodium ion battery positive electrode material and preparation method thereof | |
| WO2017063233A1 (en) | Ionic group induced compound phase modified lithium-rich layered cathode material and preparation method | |
| CN115360340A (en) | Anion-cation functionalized doped modified high-entropy polyanion type positive electrode material, preparation method and application thereof | |
| CN115832257A (en) | Lithium manganese iron phosphate positive electrode material, preparation method and application thereof | |
| CN117794854A (en) | Iron-based polyphosphate type sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN113526552B (en) | Composite positive electrode active material of lithium ion battery and preparation method thereof | |
| CN109860570A (en) | A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof | |
| CN117525391A (en) | Polyanion positive electrode material of sodium ion battery and preparation method thereof | |
| CN117457870A (en) | Vanadium manganese sodium phosphate @ graphene composite material with mesoporous-microporous structure and preparation method and application thereof | |
| CN117317190A (en) | Lithium tantalate coated lithium manganese iron phosphate positive electrode material and preparation method thereof | |
| CN116845230A (en) | Mn and Al-containing vanadium-based phosphate positive electrode material, preparation method thereof, battery and energy storage equipment | |
| CN116344763B (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN115621460B (en) | Positive electrode material and preparation method thereof | |
| CN116969434A (en) | Cr-containing vanadium-based phosphate positive electrode material, preparation method thereof, battery and energy storage equipment | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| CN115504447A (en) | Preparation method of lithium titanate coated ferric sodium pyrophosphate composite material | |
| CN114883540A (en) | Iron-based phosphate sodium-ion battery positive electrode 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |