CN115188945A - Coated positive electrode material and preparation method and application thereof - Google Patents

Coated positive electrode material and preparation method and application thereof Download PDF

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Publication number
CN115188945A
CN115188945A CN202210819334.6A CN202210819334A CN115188945A CN 115188945 A CN115188945 A CN 115188945A CN 202210819334 A CN202210819334 A CN 202210819334A CN 115188945 A CN115188945 A CN 115188945A
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sodium
positive electrode
polypropylene carbonate
solid electrolyte
equal
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赵晓兵
赵佳斌
孟庆施
戚兴国
岑波
唐堃
胡勇胜
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Beijing Zhongke Haina Technology Co ltd
Liyang Zhongke Haina Technology Co ltd
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Beijing Zhongke Haina Technology Co ltd
Liyang Zhongke Haina Technology Co ltd
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    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of sodium ion batteries, in particular to a coated positive electrode material and a preparation method and application thereof. The preparation raw material of the polypropylene carbonate solid electrolyte coated cathode material comprises a cathode active substance and a coating, wherein the coating comprises polypropylene carbonate, sodium salt and an additive. Through screening of the polymer, the polypropylene carbonate is selected as the polymer, and because the polypropylene carbonate has good oxidation resistance, the reaction of the polypropylene carbonate with a positive electrode material, particularly a charged positive electrode material, can be reduced. The polymer can be used as a solid electrolyte after being added with sodium salt and a plasticizer, and the ion diffusion coefficient of sodium ions is improved compared with that of common coating.

Description

Coated positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a coated positive electrode material and a preparation method and application thereof.
Background
Lithium ion batteries are widely applied in the aspects of people's lives at present, and with the further improvement of the control requirement of global carbon emission, the efficient utilization of clean energy further stimulates the development of secondary battery markets, particularly electric vehicles and large-scale energy storage.
The limitation of lithium resources brings sodium ion batteries into the field of people, and the sodium ion batteries also enter the initial stage of industrialization at present. The core technology of the sodium ion battery lies in the anode and cathode materials, and the capacity and the cycle of the anode material greatly influence the application of the technology at present.
The most potential layered oxide anode material at present has the defects of poor stability in air, poor stability of a circulation process and electrolyte and the like, so that the overall circulation performance is reduced. There is a need to solve the fundamental problem at the material level, thereby solving the problem of large-scale application of materials.
Technologies developed so far include an inactive oxide coating method, a sodium ion battery active oxide coating method, and a solid electrolyte coating method, in which various substances are coated on the surface of material particles, thereby improving the stability thereof. The method is most common in the technical field of batteries and is also most widely applied. Specifically, the above-mentioned substance is sufficiently mixed with the host material by a solid phase, a liquid phase or the like, and then subjected to a secondary heat treatment to obtain the clad material.
However, the coating material prepared by the prior art has certain defects: the inorganic matter coating method needs higher requirements on the particles of the inorganic matter, and usually needs to reach the nanometer scale, and the material is ground to the nanometer scale, so the dispersibility is poor, and the energy consumption is high. And the inorganic substance coating method usually needs high-temperature treatment, has high energy consumption and is not beneficial to the low-carbon development idea, and the coating agent and the main material often have chemical reaction in the high-temperature treatment process, so that the consistency of the product is poor. In addition, the inorganic coating has poor coating uniformity, and thus, more uniform and thinner coating cannot be achieved.
Disclosure of Invention
The invention aims to provide a polypropylene carbonate solid electrolyte coated positive electrode material, and a preparation method and application thereof, so as to solve the defects in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polypropylene carbonate solid electrolyte coated anode material, which comprises an anode active substance and a coating material;
the positive active material is Na x Mn i M y O 2+β Wherein M is Li + ，Cu 2+ ，Ni 2+ ，Mg 2+ ，Mn 2+ ，Zn 2+ ，Co 2+ ，Ca 2 + ，Ba 2+ ，Sr 2+ ，Mn 3+ ，Al 3+ ，B 3+ ，Fe 3+ ，Cr 3+ ，Co 3+ ，V 3+ ，Zr 4+ ，Ti 4+ ，Sn 4+ ，V 4+ ，Mo 4+ ，Mo 5+ ，Ru 4+ ，Nb 5+ ，Si 4+ ，Sb 5+ ，Nb 5+ ，Mo 6+ And Te 6+ One or more of (a);
the coating comprises polypropylene carbonate, sodium salt and an additive.
Preferably, the Na x Mn i M y O 2+β In the formula, x is more than or equal to 0.6 and less than or equal to 1.0; beta is more than or equal to minus 0.02 and less than or equal to 0.02; y is more than or equal to 0 and less than or equal to 0.8; i is more than or equal to 0.2 and less than or equal to 1,y + i =1, and the values of y and i satisfy the charge balance of the chemical formula. .
Preferably, the coating material is 0.01 to 10% by mass of the positive electrode active material.
Preferably, the sodium salt is one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium bisoxalate, sodium trifluoromethanesulfonate, sodium bisfluorosulfonylimide and sodium perchlorate, and the sodium salt accounts for 0.01-40% of the total mass of the coating.
Preferably, the additive is one or more of alumina, magnesia, titania, NASICON structure solid electrolyte and beta-alumina solid electrolyte, and the additive accounts for 0.01-20% of the total mass of the coating.
The invention also provides a preparation method of the polypropylene carbonate solid electrolyte coated anode material, which comprises the following steps:
(1) Mixing polypropylene carbonate, sodium salt, an additive and tetrahydrofuran to obtain a mixed solution;
(2) And mixing the mixed solution with a positive active substance, and drying to obtain the polypropylene carbonate solid electrolyte coated positive material.
Preferably, the mass ratio of the polypropylene carbonate to the tetrahydrofuran is 0.0893-89.286: 1000.
preferably, the drying temperature in the step (2) is 60-100 ℃.
Preferably, the drying time in the step (2) is 20 to 30 hours.
The invention also provides application of the polypropylene carbonate solid electrolyte coated positive electrode material in preparation of a sodium ion secondary battery.
The invention also provides a positive electrode for the sodium-ion battery, which comprises the positive electrode material.
The invention also provides a sodium ion battery which comprises the positive electrode.
The invention also provides a battery module comprising the sodium-ion battery.
The invention also provides a battery pack comprising the battery module.
The invention also provides a power device which comprises the sodium ion battery or the battery module or the battery pack.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the invention, an organic polymerization coating mode is adopted, the polypropylene carbonate is taken as a polymer, the polymer can be dissolved in an organic solvent, the solvent and the material are mixed and then dried, the molecular-level coating can be realized, meanwhile, the softening point of the polymer is low, and a more uniform and thinner coating layer is easy to form.
(2) According to the invention, the organic polymerization coating is dissolved in the organic solvent and then mixed with the material and dried to realize coating, high-temperature treatment and grinding treatment are not needed, and the energy consumption is reduced.
(3) The polypropylene carbonate as a polymer has good oxidation resistance, can reduce the reaction with a positive electrode material, particularly a charged positive electrode material, reduces the influence on the product performance, and has better product consistency.
(4) The polymer can be used as a solid electrolyte after sodium salt and a plasticizer are added, and compared with the common coating, the ionic diffusion coefficient and the conductivity of sodium ions are improved.
(5) By coating the polymer solid electrolyte, a uniformly coated positive electrode material can be obtained. Thereby reducing the surface activity of the material, improving the stability and electrochemical stability of the material in the air and improving the cycle performance.
Drawings
Fig. 1 is an SEM image of a positive electrode material coated with 0.01% polypropylene carbonate solid electrolyte prepared in example 1;
FIG. 2 is an SEM image of a positive electrode material coated with 0.1% polypropylene carbonate solid electrolyte prepared in example 2;
FIG. 3 is an SEM image of a 5% polypropylene carbonate coated solid electrolyte positive electrode material prepared in example 3;
FIG. 4 is an SEM image of a positive electrode material coated with 10% of a polypropylene carbonate solid electrolyte prepared in example 4;
FIG. 5 is an SEM image of a positive electrode material of an uncoated polypropylene carbonate solid electrolyte obtained in comparative example 1;
fig. 6 is a cycle test chart of the positive electrode material soft-package battery coated with the polypropylene carbonate solid electrolyte of examples 1 to 4 and a cycle test chart of the uncoated positive electrode material soft-package battery prepared in comparative example 1;
fig. 7 shows the gas production of the positive electrode material soft-package battery coated with the polypropylene carbonate solid electrolyte in examples 1-4 and the gas production of the uncoated positive electrode material soft-package battery prepared in comparative example 1.
Detailed Description
The invention provides a polypropylene carbonate solid electrolyte coated anode material, which is prepared from raw materials including an anode active substance and a coating substance;
the positive active material is Na x Mn i M y O 2+β Wherein M is Li + ，Cu 2+ ，Ni 2+ ，Mg 2+ ，Mn 2+ ，Zn 2+ ，Co 2+ ，Ca 2 + ，Ba 2+ ，Sr 2+ ，Mn 3+ ，Al 3+ ，B 3+ ，Fe 3+ ，Cr 3+ ，Co 3+ ，V 3+ ，Zr 4+ ，Ti 4+ ，Sn 4+ ，V 4+ ，Mo 4+ ，Mo 5+ ，Ru 4+ ，Nb 5+ ，Si 4+ ，Sb 5+ ，Nb 5+ ，Mo 6+ And Te 6+ One or more of (a); preferably Cu 2+ ，Ni 2+ ，Mg 2+ ，Mn 2+ ，Zn 2+ ，Co 2+ ，Ca 2+ ，Ba 2+ ，Sr 2+ ，Mn 3+ ，Al 3+ ，B 3+ ，Fe 3+ ，Cr 3+ ，Co 3+ ，V 3+ ，Zr 4+ ，Ti 4+ ，Sn 4+ ，V 4+ ，Mo 4+ ，Mo 5+ ，Ru 4+ ，Nb 5+ ，Si 4+ One or more of;
the coating comprises polypropylene carbonate, sodium salt and an additive.
In the present invention, the polypropylene carbonate is available from michelin, cat #: p886227.
In the present invention, the Na is x Mn i M y O 2+β In the formula, x is more than or equal to 0.6 and less than or equal to 1.0, beta is more than or equal to 0.02 and less than or equal to 0.02, preferably x is more than or equal to 0.7 and less than or equal to 0.8, and beta is more than or equal to 0.01 and less than or equal to 0.01; y is more than or equal to 0 and less than or equal to 0.8; i is more than or equal to 0.2 and less than or equal to 1, preferably y is more than or equal to 0.2 and less than or equal to 0.5, and i is more than or equal to 0.5, and y + i =1, and the values of y and i satisfy the charge balance of the chemical formula.
In the invention, the x, y, i and beta are respectively the mole percentage of the corresponding elements, and the molecular formula can reach electric neutrality.
In the present invention, the coating material is 0.01 to 10% by mass, preferably 5 to 10% by mass of the positive electrode active material.
In the invention, the sodium salt is one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium bisoxalate, sodium trifluoromethanesulfonate, sodium bisfluorosulfonylimide and sodium perchlorate, preferably one or more of sodium trifluoromethanesulfonate, sodium bisfluorosulfonylimide and sodium perchlorate; the sodium salt accounts for 0.01 to 40 percent of the total mass of the coating, and preferably 10 to 20 percent.
In the invention, the additive is one or more of alumina, magnesia, titania, NASICON structure solid electrolyte and beta-alumina solid electrolyte, preferably one or more of alumina, magnesia and titania, and the additive accounts for 0.01-20%, preferably 0.5-5% of the total mass of the coating.
The invention also provides a preparation method of the polypropylene carbonate solid electrolyte coated anode material, which comprises the following steps:
(1) Mixing polypropylene carbonate, sodium salt, an additive and tetrahydrofuran to obtain a mixed solution;
(2) And mixing the mixed solution with a positive active substance, and drying to obtain the polypropylene carbonate solid electrolyte coated positive material.
In the invention, the mass ratio of the polypropylene carbonate to the tetrahydrofuran is 0.0893-89.286: 1000, preferably 0.893 to 89.286:1000.
in the present invention, the drying in step (2) is vacuum drying, and the temperature is preferably 60 to 100 ℃, more preferably 65 to 80 ℃, and the time is preferably 18 to 30 hours, more preferably 22 to 26 hours.
The invention also provides a positive electrode for the sodium-ion battery, which comprises the positive electrode material.
The invention also provides a sodium ion battery which comprises the positive electrode.
The invention also provides a battery module comprising the sodium-ion battery.
The invention also provides a battery pack which comprises the battery module.
The invention also provides a power device which comprises the sodium ion battery or the battery module or the battery pack.
In the invention, the sodium ion secondary battery anode material is used for electric tools, electric vehicles, photovoltaic power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or energy storage equipment of communication base stations.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 0.0893g of polypropylene carbonate is dissolved in 1000g of tetrahydrofuran, 0.00892g of sodium bis (fluorosulfonyl) imide and 0.00178g of alumina are added, and the mixture is fully stirred to obtain a mixed solution;
(2) 1kg of NaNi as a positive electrode material was added to the mixed solution 1/3 Fe 1/3 Mn 1/3 O 2 Stirring and evaporating to dryness, and after tetrahydrofuran is evaporated to dryness, performing vacuum drying for 24 hours at the temperature of 100 ℃ to obtain the positive electrode material with the coating material coated by the polypropylene carbonate solid electrolyte of which the proportion is 0.01%.
Example 2
(1) Dissolving 0.893g of polypropylene carbonate in 1000g of tetrahydrofuran, adding 0.0892g of sodium bis (fluorosulfonyl) imide and 0.0178g of alumina, and fully stirring to obtain a mixed solution;
(2) 1kg of NaNi as a positive electrode material was added to the mixed solution 1/3 Fe 1/3 Mn 1/3 O 2 Stirring and evaporating to dryness, and after tetrahydrofuran is evaporated to dryness, performing vacuum drying for 24 hours at the temperature of 100 ℃ to obtain the positive electrode material with the coating material coated by the polypropylene carbonate solid electrolyte and the proportion of 0.1%.
Example 3
(1) 44.643g of polypropylene carbonate is dissolved in 1000g of tetrahydrofuran, 4.464g of sodium bis (fluorosulfonyl) imide and 0.893g of alumina are added, and the mixture is fully stirred to obtain a mixed solution;
(2) 1kg of NaNi as a positive electrode material was added to the mixed solution 1/3 Fe 1/3 Mn 1/3 O 2 Stirring and evaporating to dryness, and after tetrahydrofuran is evaporated to dryness, performing vacuum drying for 24 hours at the temperature of 100 ℃ to obtain the positive electrode material with the coating material coated by the polypropylene carbonate solid electrolyte of which the proportion is 5%.
Example 4
(1) 89.286g of polypropylene carbonate is dissolved in 1000g of tetrahydrofuran, 8.9283g of sodium bis (fluorosulfonyl) imide and 1.7857g of alumina are added, and the mixture is fully stirred to obtain a mixed solution;
(2) 1kg of NaNi as a positive electrode material was added to the mixed solution 1/3 Fe 1/3 Mn 1/3 O 2 Stirring and evaporating to dryness, and after tetrahydrofuran is evaporated to dryness, performing vacuum drying for 24 hours at the temperature of 100 ℃ to obtain the positive electrode material with the coating material coated by the polypropylene carbonate solid electrolyte of which the proportion is 10%.
Comparative example 1
Comparative example 1 is different from example 1 in that a cathode material which is not coated with a coating comprising a polypropylene carbonate solid electrolyte is used.
The positive electrode materials obtained in examples 1 to 4 and comparative example 1 were assembled into a flexible packaging cell, and the cycle performance and the gas generation condition (room temperature) were tested, and the cycle test results are shown in table 1 and fig. 5, and the gas generation condition is shown in table 1 and fig. 6.
Table 1 cycle test results and gas generation conditions of soft package cells assembled from positive electrode materials obtained in examples 1 to 3 and comparative example 1
Figure BDA0003743536990000071
Fig. 1 is an SEM image of the positive electrode material coated with 0.01% polypropylene carbonate solid electrolyte prepared in example 1, and it can be seen from the SEM image that there are dotted coating objects sporadically on the surface of the material, which cover most of the area even though not dense, and reduce the contact area between the surface of the positive electrode material and the electrolyte solution, which causes side reaction;
FIG. 2 is an SEM image of a 0.1% polypropylene carbonate solid electrolyte coated positive electrode material prepared in example 2, wherein a layer of substance is partially coated on the surface of the material;
FIG. 3 is an SEM image of the 5% polypropylene carbonate coated solid electrolyte prepared in example 3, wherein the surface of the material is almost covered by the coating material, and only a small part of the surface of the substrate is exposed;
FIG. 4 is an SEM image of the positive electrode material coated with 10% of polypropylene carbonate solid electrolyte prepared in example 4, wherein the surface of the material is completely covered by the coating material to form a compact surface coating layer;
fig. 5 is an SEM image of the positive electrode material uncoated with the polypropylene carbonate solid electrolyte obtained in comparative example 1, and it can be seen from the image that the surface of the material is completely exposed, and side reaction with the electrolyte is easily generated in the battery, resulting in failure of the material.
As can be seen from table 1 and fig. 6, the cycle performance of the soft-package battery cell assembled by the coated positive electrode material is greatly improved, and as can be seen from table 1 and fig. 7, the gas production of the soft-package battery cell assembled by the coated positive electrode material is obviously reduced, and when the coating proportion is 10%, the cycle performance and the gas production condition are both optimal.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The positive electrode material coated with the polypropylene carbonate solid electrolyte is characterized in that raw materials for preparing the positive electrode material comprise a positive electrode active substance and a coating material;
the positive active material is Na x Mn i M y O 2+β Wherein M is Li + ，Cu 2+ ，Ni 2+ ，Mg 2+ ，Mn 2+ ，Zn 2+ ，Co 2+ ，Ca 2+ ，Ba 2 + ，Sr 2+ ，Mn 3+ ，Al 3+ ，B 3+ ，Fe 3+ ，Cr 3+ ，Co 3+ ，V 3+ ，Zr 4+ ，Ti 4+ ，Sn 4+ ，V 4+ ，Mo 4+ ，Mo 5+ ，Ru 4+ ，Nb 5+ ，Si 4+ ，Sb 5+ ，Nb 5+ ，Mo 6+ And Te 6+ One or more of;
the coating comprises polypropylene carbonate, sodium salt and an additive.
2. The polypropylene carbonate solid electrolyte coated cathode material as claimed in claim 1, characterized in that the Na is x Mn i M y O 2+β In the formula, x is more than or equal to 0.6 and less than or equal to 1.0; beta is more than or equal to minus 0.02 and less than or equal to 0.02; y is more than or equal to 0 and less than or equal to 0.8; i is more than or equal to 0.2 and less than or equal to 1,y + i =1, and the values of y and i satisfy the charge balance of the chemical formula; the mass of the coating is 0.01-10% of that of the positive active material.
3. The polypropylene carbonate solid electrolyte coated cathode material according to claim 1 or 2, wherein the sodium salt is one or more of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium bisoxalate, sodium trifluoromethylsulfonate, sodium bisfluorosulfonylimide and sodium perchlorate, and the sodium salt accounts for 0.01 to 40% of the total mass of the coating;
the additive is one or more of alumina, magnesia, titanium oxide, NASICON structure solid electrolyte and beta-alumina solid electrolyte, and accounts for 0.01-20% of the total mass of the coating.
4. A method for preparing a polypropylene carbonate solid electrolyte coated positive electrode material according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing polypropylene carbonate, sodium salt, an additive and tetrahydrofuran to obtain a mixed solution;
(2) And mixing the mixed solution with a positive active substance, and drying to obtain the polypropylene carbonate solid electrolyte coated positive material.
5. The preparation method of the polypropylene carbonate solid electrolyte coated cathode material as claimed in claim 4, wherein the mass ratio of the polypropylene carbonate to the tetrahydrofuran is 0.0893-89.286: 1000, parts by weight; the drying temperature in the step (2) is 60-100 ℃, and the drying time is 20-30 h.
6. A positive electrode for a sodium-ion battery, comprising the positive electrode material according to any one of claims 1 to 3.
7. A sodium ion battery comprising the positive electrode according to claim 6.
8. A battery module comprising the sodium-ion battery of claim 7.
9. A battery pack comprising the battery module according to claim 8.
10. A power plant comprising a sodium-ion battery or battery module or battery pack according to any one of claims 7 to 9.
CN202210819334.6A 2022-07-13 2022-07-13 Coated positive electrode material and preparation method and application thereof Pending CN115188945A (en)

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Cited By (1)

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CN116454285A (en) * 2023-06-16 2023-07-18 中节能万润股份有限公司 Method for reducing residual alkali on surface of layered positive electrode material of sodium ion battery and application

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CN116454285A (en) * 2023-06-16 2023-07-18 中节能万润股份有限公司 Method for reducing residual alkali on surface of layered positive electrode material of sodium ion battery and application

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