CN114361415A - Sodium ion battery anode material with multi-core type core-shell structure and preparation method thereof - Google Patents

Sodium ion battery anode material with multi-core type core-shell structure and preparation method thereof Download PDF

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CN114361415A
CN114361415A CN202111636665.8A CN202111636665A CN114361415A CN 114361415 A CN114361415 A CN 114361415A CN 202111636665 A CN202111636665 A CN 202111636665A CN 114361415 A CN114361415 A CN 114361415A
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core
ion battery
positive electrode
shell
sodium
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杨张萍
韩珽
陈英
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Zhejiang Meidarui New Material Technology Co ltd
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Priority to PCT/CN2022/123978 priority patent/WO2023124356A1/en
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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
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The positive electrode material of the sodium ion battery with the multi-core-shell structure comprises a plurality of particles, wherein each particle comprises a core and a shell covering the outer side of the core. The core is composed of a plurality of cores and a gap exists between any two adjacent cores in the plurality of cores. A plurality of the inner cores are made of two or more than two nanoscale particle materials with the same or different structures. The nano-scale particle material is one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large-frame compound material. The positive electrode material of the sodium-ion battery can realize advantage complementation of structure and performance on a nanoscale layer and make up for defects, and can better exert the due advantages compared with the simple mixed application of coating on an electrode plate. The invention also provides a preparation method of the positive electrode material of the sodium-ion battery.

Description

Sodium ion battery anode material with multi-core type core-shell structure and preparation method thereof
Technical Field
The invention belongs to the field of sodium ion batteries, and particularly relates to a positive electrode material of a sodium ion battery with a multi-core type core-shell structure and a preparation method thereof.
Background
At present, lithium ion batteries are widely applied to products such as mobile phones, cameras, notebook computers, electric tools, electric bicycles, electric automobiles and the like because of the advantages of high specific capacity, high voltage, good safety performance and the like. However, the growing market of lithium ion batteries inevitably brings about the problems of lithium resource shortage and lithium price rise, and the sodium ion battery system has abundant resources, low price, environmental friendliness and similar electrochemical properties with the lithium ion battery, so that the sodium ion battery system is widely concerned in recent years, and a new choice is provided for electrochemical energy storage. However, sodium ions have larger ionic radius and slower kinetic rate, which become main factors restricting the development of energy storage materials, and the development of high-performance sodium-insertion cathode materials is the key to improve the specific energy of sodium ion batteries and promote the application thereof.
The positive electrode material system currently studied by sodium ion batteries comprises transition metal oxides, polyanion materials, Prussian blue compounds, organic molecules, polymers, amorphous materials and the like. Transition metal oxides can be classified into tunnel type oxides and layered oxides according to the structure of the positive electrode material. The layered metal oxide has a high capacity and a high charge/discharge voltage, but the structure is unstable. In the case of tunnel metal oxide, the structure is stable, but the reversible capacity and the cycle performance are poor. Polyanion compounds are also stable in structure, but have low electron conductivity and low volumetric energy density. For prussian blue compounds, the voltage and reversible capacity are high, the cost is low, the cycle stability is poor, and the prussian blue compounds are easily decomposed by heating at high temperature. Finally, for organic compounds and polymers, the theoretical specific capacity is high, the raw materials are rich, the environment is friendly, the price is low, the structural design is flexible, but the voltage is low, the organic compound and the polymer are easy to dissolve in electrolyte, and the circulation stability is poor. It can thus be seen that it is difficult to obtain excellent properties from a single material.
In the prior art, in order to improve the electrochemical performance of a sodium-insertion cathode material, a common method is to perform structural doping modification, surface coating modification and the like on the cathode material. However, the simple coating and doping of a sodium-insertion cathode material cannot achieve a satisfactory effect, and the modification cost of a sodium-insertion cathode material is relatively high, so that the method is far away from the scale production and the final industrialization at present.
In industry, two or more than two anode materials are generally mixed and coated on the pole piece according to specific needs, and the advantages of the two or more than two different materials are complemented to achieve the purposes of optimizing various electrochemical indexes and saving cost. However, this method has a disadvantage in that the plurality of positive electrode materials coated on the electrode sheet are independent and only macroscopically mixed, which may cause non-uniformity of each performance index, and thus may not be expected.
Disclosure of Invention
In view of the above, the invention provides a sodium ion battery anode material with a multi-core-shell structure and a preparation method thereof. The positive electrode material of the sodium ion battery with the multi-core type core-shell structure consists of a core consisting of a plurality of cores and a shell contained in one shell. The core may be composed of two or more materials, the structures of which may be the same or different, and the cores are contained together in one shell, so that the materials may complement the advantages of structure and properties at the nanoscale level, rather than simply mix, so that the composition and properties are uniformly distributed at the nanoscale. And micro gaps exist among the cores, and the uniformly distributed space can provide buffer space for the change of the crystal lattice size of Na + in the de-intercalation process and buffer the volume change caused by the expansion and contraction of the material during the temperature change, so that the cycle performance is improved, and the thermal stability and the safety are improved; the uniform and tiny gaps also increase transmission channels for Na + on the surfaces of the grains, thereby improving the electrochemical performance, particularly the rate performance.
The positive electrode material of the sodium ion battery with the multi-core-shell structure comprises a plurality of particles, wherein each particle comprises a core and a shell coated on the outer side of the core. The core is composed of a plurality of cores and a gap exists between any two adjacent cores in the plurality of cores. A plurality of the inner cores are made of two or more than two nanoscale particle materials with the same or different structures. The nano-scale particle material is one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large-frame compound material.
Further, the layerThe material with the structure is NaxMeO2Wherein 0.5<x<1.8, Me is one or more of nickel, cobalt, aluminum, manganese, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium, lanthanide, yttrium, scandium, sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine, astatine.
Further, the tunnel structure material is NaxMeO2Wherein 0 is<x is less than or equal to 0.5, Me is one or more of nickel, cobalt, aluminum, manganese, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium, lanthanide elements, yttrium, scandium, sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine and astatine.
Further, the polyanion compound is NaxMy[(XmOn)]zWherein X is not less than 0, y is not less than 1, M is not less than 1, n is not less than 4, z is not less than 1, M is metal ion with variable valence state, and X is at least one element of phosphorus, sulfur, vanadium, silicon, boron, arsenic, selenium, tellurium, fluorine, iodine, astatine and the like.
Further, the element M is at least one element of nickel, cobalt, manganese, iron, vanadium, titanium, magnesium and the like.
Further, the large framework compound is NaxMa[Mb(CN)6]y·zH2O, wherein x is more than or equal to 0 and less than or equal to 9 and 0<y<Z is more than or equal to 0 and less than or equal to 4, and Ma and Mb are transition metal ions.
Further, the transition metal ions are one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold and mercury.
Further, the material from which the plurality of cores is made is in any stoichiometric ratio.
Further, the material of the case is inert with respect to the battery electrolyte.
The preparation method of the sodium ion battery anode material with the multi-core type core-shell structure comprises the following steps:
STEP 101: respectively providing at least two nanoscale particle materials and a binder for preparing a core, and fully stirring and uniformly mixing the materials and the binder according to a certain stoichiometric ratio to form a mixture, wherein the materials are one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large framework compound material;
STEP 102: after spray drying the obtained mixture, the nanoparticles formed by the different materials are physically bonded together into a core consisting of a plurality of inner cores;
STEP 103: providing a shell material for preparing a shell, dissolving the shell material in a solvent to form a shell solution, fully stirring the shell solution to wrap the shell material on the surface of a core, and filtering, washing and drying the shell solution to form a blank of the positive electrode material of the sodium-ion battery;
STEP 104: and (2) calcining the blank of the positive electrode material of the sodium-ion battery at high temperature or carrying out heat treatment for a period of time, and then cooling, crushing and sieving to obtain the positive electrode material of the sodium-ion battery.
Compared with the prior art, the sodium ion battery anode material with the multi-core type core-shell structure has the following beneficial effects:
(1) the core of the positive electrode material of the sodium-ion battery consists of the inner cores made of two or more than two materials, so that the components and various properties of the core are uniformly distributed on a nanometer scale, the advantages of the structure and the properties can be complemented and the defects can be compensated on the nanometer level, and the due advantages of the positive electrode material can be better exerted compared with the method that the positive electrode material is simply mixed and coated on an electrode plate.
(2) In the multi-core structure provided by the invention, the micro gaps exist among the cores, and the more uniformly distributed space can provide a buffering space for the change of the lattice size of Na + in the de-intercalation process, so that the deformation of the structure during charging and discharging can be reduced, the possibility of collapse inside the structure is reduced, and the cycle performance of the material is further improved.
(3) The micro-gaps in the multi-core structure can also provide buffer for volume change generated by expansion and contraction of the material during temperature change, so that the thermal stability and safety of the material are improved.
(4) Meanwhile, the uniform and tiny gaps also increase transmission channels for Na < + > on the surfaces of the grains, so that the electrochemical performance is improved, and particularly the rate capability of the material is improved.
Drawings
Fig. 1 is a schematic structural diagram of a sodium ion battery cathode material with a multi-core-shell structure provided by the invention.
FIG. 2 is a flow chart of a preparation method of the sodium ion battery anode material with a multi-core type core-shell structure provided by the invention.
Fig. 3 is a first charge-discharge curve diagram of the sodium-ion battery positive electrode material with the multi-core-shell structure of example 1.
Fig. 4 is a cycle charge/discharge curve diagram of the sodium ion battery positive electrode material of the multicore core-shell structure of example 1.
Detailed Description
Specific examples of the present invention will be described in further detail below. It should be understood that the description herein of embodiments of the invention is not intended to limit the scope of the invention.
As shown in fig. 1, the sodium ion battery positive electrode material with a multi-core-shell structure provided by the present invention includes a plurality of particles 10. Each granule 10 comprises a core 11 and a shell 12 covering the outside of the core 11. The core 11 is composed of a plurality of cores 111 and a gap exists between any two adjacent cores 111 of the plurality of cores 111. A plurality of the inner cores 111 are made of two or more kinds of nano-sized particle materials of the same or different structures. The nano-scale particle material is one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large-frame compound material. The layered structure material is the technical content disclosed in the prior art, such as a layered cobalt-based sodium ion battery cathode material disclosed in Chinese patent application No. 202010792950.8, and a preparation method and application thereof. In this embodiment, the layersThe material with the structure is NaxMeO2Wherein 0.5<x<1.8, Me is one or more of nickel, cobalt, aluminum, manganese, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium, lanthanide, yttrium, scandium, sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine, astatine. Specifically, the layered structure material may be one or more of copper iron sodium manganate, nickel copper manganese sodium ferrite, nickel cobalt sodium aluminate, magnesium sodium manganese, and sodium nickel ferrite. The tunnel structure material is also the prior art, and is a technical scheme used in a preparation method of a water system sodium ion battery positive electrode composite material disclosed in Chinese patent application No. 201710891377.4. In this embodiment, the tunnel structure material is NaxMy[(XmOn)]zWherein X is more than or equal to 0, y is more than or equal to 1, M is more than or equal to 1, n is more than or equal to 4, z is more than or equal to 1, M is metal ions with variable valence states, and X is at least one or more of elements such as phosphorus, sulfur, vanadium, silicon, boron, arsenic, selenium, tellurium, fluorine, iodine, astatine and the like. Specifically, the tunnel structure material is one or more of sodium manganate, sodium nickelate, sodium titanium manganese oxide, sodium cobaltate and the like. The polyanionic compound is also the prior art, such as a vanadium manganese sodium phosphate electrode material disclosed in Chinese patent application No. 201710358529.4, and a preparation method and a technical scheme disclosed in application thereof. In this embodiment, the polyanionic compound is NaxMy[(XmOn)]z(X is more than or equal to 0, y is more than or equal to 1, M is more than or equal to 1, n is more than or equal to 4, z is more than or equal to 1M and is at least one element of elements such as nickel, cobalt, manganese, iron, vanadium, titanium, magnesium and the like, and X is at least one element of elements such as phosphorus, sulfur, vanadium, silicon, boron, arsenic, selenium, tellurium, fluorine, iodine, astatine and the like) or a mixture of more than or equal to one element of elements such as NaFePO4、Na3V2(PO4)3、Na3(VOPO4)2F、Na3V2(PO4)2F3、Na2FePO4F、Na2FeP2O7、Na2MnP2O7、Na2Fe0.5Mn0.5P2O7、Na2.4Fe1.8(SO4)3、Na4Fe3(PO4)2(P2O7)、Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7And the like. The large-frame compound material is also the prior art, such as a Prussian blue type sodium ion battery positive electrode material disclosed in Chinese patent application No. 201710217961.1 and a technical scheme disclosed by a preparation method thereof. In this embodiment, the material of the macroframe compound is NaxMa[Mb(CN)6]y·zH2O, wherein x is more than or equal to 0 and less than or equal to 9 and 0<y<3，0≤z≤4，MaAnd MbAre transition metal ions. The transition metal can be one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury and the like. In particular, the macroframework compound material may be Na2MnFe(CN)6、NaFeFe(CN)6、Na1.6Co[Fe(CN)6]0.9 2.9H2O、Na2Ni0.4Co0.6Fe(CN)6、Na2NiFe(CN)6One or more of them. The material in the plurality of the inner cores 111 made of two or more kinds of nano-sized particle materials of the same or different structures is in an arbitrary stoichiometric ratio to achieve a simple manufacturing method. Since the plurality of cores 111 are composed of two or more materials, the structures of the materials may be the same or different, and the cores 111 are contained together in one case 12, so that the plurality of materials can realize advantageous complementation of the structure and performance at a nano-scale level, rather than simple mixing. In addition, the material for manufacturing the inner core 111 is nano-scale particles, so that the components and various properties are uniformly distributed in a nano-scale mode, and the consistency of the positive electrode material of the sodium-ion battery is good.
The housing 12 may be made of any material known to be useful for making an outer casing of a positive electrode material, and preferably the material of the housing 12 should be inert with respect to the battery electrolyte to avoid corrosion. The thickness of the shell is 10 nm-200 nm. More preferably, the thickness of the case is 30nm to 60 nm.
As shown in fig. 2, the invention also provides a preparation method of the sodium ion battery cathode material with the multi-core-shell structure, which comprises the following steps:
STEP 101: respectively providing at least two nanoscale particle materials and a binder for preparing the inner core 111, and fully stirring and uniformly mixing the nanoscale particle materials and the binder to form a mixture according to a certain stoichiometric ratio, wherein the nanoscale particle materials are one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large framework compound material;
STEP 102: after spray-drying the obtained mixture, the nanoparticles formed of different materials are physically bound together into a core 11 consisting of a plurality of inner cores 111;
STEP 103: providing a shell material for preparing a shell 12, dissolving the shell material in a solvent to form a shell solution, fully stirring the shell solution to enable the shell material to be wrapped on the surface of a core 11, and filtering, washing and drying the shell solution to form a blank of the positive electrode material of the sodium-ion battery;
STEP 104: and (2) calcining the blank of the positive electrode material of the sodium-ion battery at high temperature or carrying out heat treatment for a period of time, and then cooling, crushing and sieving to obtain the positive electrode material of the sodium-ion battery.
In STEP101, the size of the core 11 is controlled by adjusting the composition and amount of the binder. The total particle size of the prepared core 11 is 100nm to 25 um. More preferably, the total particle size of the core is 100-10 um.
In STEP103, the thickness of the housing 12 can be adjusted as needed, depending on experimental conditions. Preferably, the thickness is on the order of nanometers. The solvent may be an aluminum isopropoxide ethanol solution.
In STEP104, the binder is removed by calcination, so that gaps are formed between the nano-sized particles used to prepare the inner core 111 to provide a buffer space for changes in lattice size during Na + deintercalation and also for volume changes caused by expansion and contraction of the material upon temperature change.
Compared with the prior art, the sodium ion battery anode material with the multi-core type core-shell structure has the following beneficial effects:
(1) the core of the positive electrode material of the sodium-ion battery consists of the inner cores made of two or more than two materials, so that the components and various properties of the core are uniformly distributed on a nanometer scale, the advantages of the structure and the properties can be complemented and the defects can be compensated on the nanometer level, and the due advantages of the positive electrode material can be better exerted compared with the method that the positive electrode material is simply mixed and coated on an electrode plate.
(2) In the multi-core structure provided by the invention, the micro gaps exist among the cores, and the more uniformly distributed space can provide a buffering space for the change of the lattice size of Na + in the de-intercalation process, so that the deformation of the structure during charging and discharging can be reduced, the possibility of collapse inside the structure is reduced, and the cycle performance of the material is further improved.
(3) The micro-gaps in the multi-core structure can also provide buffer for volume change generated by expansion and contraction of the material during temperature change, so that the thermal stability and safety of the material are improved.
(4) Meanwhile, the uniform and tiny gaps also increase transmission channels for Na < + > on the surfaces of the grains, so that the electrochemical performance is improved, and particularly the rate capability of the material is improved.
Example 1：
Copper iron sodium manganate NaCu with layered structure0.4Fe0.3Mn0.3O2Sodium ferric phosphate NaFePO with olivine structure4The nano-scale material is fully mixed according to the stoichiometric ratio of 1:0.1, the mixture is dispersed in ethanol solution containing 2.5 wt.% of aluminum isopropoxide after spray drying and nucleation, the mixture is filtered, washed and dried after 3 hours of continuous stirring, and the obtained mixture is heated to 400 DEG CCalcining for 8 hours in an argon atmosphere at the temperature, and cooling to obtain the cathode material.
The electrochemical performance of the material is tested by adopting a blue battery testing system at 25 ℃, and the testing voltage range is 2.5V-4.2V; specific capacity test conditions: charging and discharging once at 0.1C; charging and discharging once at 0.2C; 0.2C charged, 1C once discharged, as shown in fig. 3; cycle performance test conditions: the charge and discharge were performed at a rate of 1C, and the cycle was repeated for 500 weeks to examine the capacity retention rate. The specific discharge capacity of the material at the rate of 0.1C is 131 mAh/g. The capacity retention rate is more than 98% in 500 cycles of 1C charge-discharge, and the cycle performance is better, as shown in figure 4.
Example 2:
copper iron sodium manganate NaCu with layered structure0.4Fe0.3Mn0.3O2Polyanion compound Na with framework structure3V2(PO4)3The nano-scale material is fully mixed according to the stoichiometric ratio of 1:0.2, the mixture is dispersed in an ethanol solution containing 5 wt.% of aluminum isopropoxide after spray drying and nucleation, the mixture is filtered, washed and dried after being continuously stirred for 3 hours, the obtained mixture is calcined for 6 hours at the temperature of 650 ℃ in an argon atmosphere, and the anode material is obtained after cooling.
The electrochemical performance of the material is tested by adopting a blue battery testing system at 25 ℃, and the testing voltage range is 2.5V-4.2V; specific capacity test conditions: charging and discharging once at 0.1C; charging and discharging once at 0.2C; 0.2C charge, 1C discharge once; cycle performance test conditions: the charge and discharge were performed at a rate of 1C, and the cycle was repeated for 500 weeks to examine the capacity retention rate. The specific discharge capacity of the material at the rate of 0.1C is 140 mAh/g. The capacity retention rate of the 1C charge-discharge cycle for 500 weeks is more than 96%, and the cycle performance is good.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, and any modifications, equivalents or improvements that are within the spirit of the present invention are intended to be covered by the following claims.

Claims (10)

1. The positive electrode material of the sodium ion battery with the multi-core type core-shell structure is characterized in that: the positive electrode material of the sodium ion battery with the multi-core-shell structure comprises a plurality of particles, each particle comprises a core and a shell covering the outer side of the core, the core is composed of a plurality of cores, a gap is formed between any two adjacent cores in the cores, the cores are made of two or more than two nanoscale particle materials with the same or different structures, and the nanoscale particle materials are one or more than one of a layered structure material, a tunnel structure material, a polyanion compound and a large framework compound material.
2. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the material with a layered structure is NaxMeO2Wherein 0.5<x<1.8, Me is one or more of nickel, cobalt, aluminum, manganese, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium, lanthanide, yttrium, scandium, sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine, astatine.
3. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the tunnel structure material is NaxMeO2Wherein 0 is<x is less than or equal to 0.5, Me is one or more of nickel, cobalt, aluminum, manganese, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium, lanthanide elements, yttrium, scandium, sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine and astatine.
4. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the polyanion compound is NaxMy[(XmOn)]zWherein X is more than or equal to 0, y is more than or equal to 1, M is more than or equal to 1, n is more than or equal to 4, z is more than or equal to 1, M is metal ion with variable valence, X is phosphorus, sulfur, vanadium,At least one element selected from the group consisting of silicon, boron, arsenic, selenium, tellurium, fluorine, iodine, astatine, and the like.
5. The sodium ion battery cathode material with the multi-core-shell structure according to claim 4, wherein: the element M is at least one element of nickel, cobalt, manganese, iron, vanadium, titanium, magnesium and the like.
6. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the large framework compound is NaxMa[Mb(CN)6]y·zH2O, wherein x is more than or equal to 0 and less than or equal to 9 and 0<y<Z is more than or equal to 0 and less than or equal to 4, and Ma and Mb are transition metal ions.
7. The sodium ion battery cathode material with the multi-core-shell structure according to claim 6, wherein: the transition metal ions are one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold and mercury.
8. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the material from which the plurality of cores is made is in any stoichiometric ratio.
9. The sodium ion battery positive electrode material with the multi-core-shell structure according to claim 1, which is characterized in that: the material of the housing is inert with respect to the battery electrolyte.
10. A preparation method of a sodium ion battery anode material with a multi-core type core-shell structure comprises the following steps:
STEP 101: respectively providing at least two nanoscale particle materials and a binder for preparing a core, and fully stirring and uniformly mixing the materials and the binder according to a certain stoichiometric ratio to form a mixture, wherein the materials are one or more of a layered structure material, a tunnel structure material, a polyanion compound and a large framework compound material;
STEP 102: after spray drying the obtained mixture, the nanoparticles formed by the different materials are physically bonded together into a core consisting of a plurality of inner cores;
STEP 103: providing a shell material for preparing a shell, dissolving the shell material in a solvent to form a shell solution, fully stirring the shell solution to wrap the shell material on the surface of a core, and filtering, washing and drying the shell solution to form a blank of the positive electrode material of the sodium-ion battery;
STEP 104: and (2) calcining the blank of the positive electrode material of the sodium-ion battery at high temperature or carrying out heat treatment for a period of time, and then cooling, crushing and sieving to obtain the positive electrode material of the sodium-ion battery.
CN202111636665.8A 2021-12-29 2021-12-29 Sodium ion battery anode material with multi-core type core-shell structure and preparation method thereof Pending CN114361415A (en)

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