CN117810379A - Sodium battery composite positive electrode material and application thereof - Google Patents
Sodium battery composite positive electrode material and application thereof Download PDFInfo
- Publication number
- CN117810379A CN117810379A CN202211166710.2A CN202211166710A CN117810379A CN 117810379 A CN117810379 A CN 117810379A CN 202211166710 A CN202211166710 A CN 202211166710A CN 117810379 A CN117810379 A CN 117810379A
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- China
- Prior art keywords
- positive electrode
- sodium
- core
- coating layer
- composite positive
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- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 204
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
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- 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
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- H—ELECTRICITY
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- 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
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- 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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- 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
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- 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
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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
- H01M4/48—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
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- 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
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The embodiment of the application provides a sodium battery composite positive electrode material and application thereof, wherein the composite positive electrode material comprises an inner core and a coating layer for coating the inner core, the inner core comprises a layered sodium positive electrode active material, the sodium removal potential of the coating layer material is higher than that of the inner core, and the composite positive electrode material comprises a general formula Na m E a J b G c O n The substances shown in the general formula Na d R e Q f F g The substances shown, na 3 V(PO 3 ) 3 At least one of N; 0<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises at least one of Ga, ge, as, se, in, sn, sb, te, tl, bi, and G comprises at least one of Li, mg, zn, ru, ir; 0<d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R is a metal element, and Q represents a polyanion group. The composite positive electrode material has good air stability and higher specific capacity.
Description
Technical Field
The embodiment of the application relates to the technical field of sodium batteries, in particular to a sodium battery composite positive electrode material and application thereof.
Background
The sodium ion battery is a battery with a similar energy storage mechanism as the lithium ion battery, and because the sodium resource is abundant in reserves on the earth, the raw material cost of the sodium ion battery is far lower than that of lithium, so the sodium ion battery is more hopeful to meet the low-cost requirement of a large-scale energy storage device in the future, and as a key composition of the sodium ion battery, the performance of a sodium positive electrode material has an important influence on the performance of the sodium ion battery.
Wherein the common layered sodium cathode material is susceptible to water and CO in humid air 2 A large amount of residual alkali and even phase structure change can be generated on the surface, and the processing performance and electrochemical performance of the product are affected. Among them, surface coating modification of the layered sodium positive electrode material is one of the common means for improving the air stability thereof. Common coating materials are typically alkali-residue-consumable materials, such as solid electrolyte materials, which, while reducing the initial alkali residue, are deficient in water and CO due to the coating itself 2 The effective defense of the kernel is enabled to continuously generate residual alkali in the laying process; in addition, most of the coating is not electrochemically active, e.g. solid electrolyte-like materials, although Na is provided + The transmission channel cannot contribute gram capacity, and the specific capacity of the positive electrode material is easily reduced.
Therefore, there is a need to develop a coating material that can achieve both good air stability and electrochemical activity to better enhance the performance of the layered sodium cathode material.
Disclosure of Invention
In view of this, the embodiment of the application provides a core-shell type sodium battery composite positive electrode material and application thereof, so as to improve the air stability of a core material and endow the composite positive electrode material with good storage and processing performances and good electrochemical performances on the premise of not reducing the gram capacity of the core layered sodium positive electrode material.
The first aspect of the embodiment of the application provides a sodium battery composite positive electrode material, which comprises an inner core and a coating layer coated on the inner core, wherein the inner core comprises a layered sodium positive electrode active material, the material of the coating layer is a high-voltage type sodium active material with sodium removal potential higher than that of the inner core, and the high-voltage type sodium active material comprises a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 At least one of N; wherein 0 is<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga, ge, as, se, in, sn, sb, te, tl, B, and G comprises one or more of Li, mg, zn, ru, ir; 0<d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R represents a metal element, Q represents a polyanion group, and F represents a fluorine element.
In the composite positive electrode material, the coating layer is arranged on the surface of the layered sodium positive electrode active material, and the air stability of the sodium-containing positive electrode material is directly related to the charging potential of the sodium-containing positive electrode material, so that the higher the charging potential is, the better the air stability is, the better the stability of the coating layer with higher sodium-removing potential in humid air is, the direct contact between the core material and the humid air can be reduced, the air stability of the core is improved, and the structural change and the electrochemical performance reduction of the core are prevented; meanwhile, the coating layer has sodium electrochemical activity, can contribute to capacity in a charge-discharge voltage window of the core material, and cannot reduce gram capacity of the core material.
In this embodiment, the high voltage type sodium active material has a 0.2V higher sodium removal potential than the core.
In an embodiment of the present application, the high voltage type sodium active material has a sodium removal potential of 3.3V or more.
In this embodiment, in the working voltage range of the inner core, the discharge gram capacity of the coating layer material is 50% -70% of the discharge gram capacity of the inner core. Thus, the coating layer not only contributes to a certain capacity, but also can not excessively remove sodium, and can reduce the unit cell volume change of the inner core under a high voltage window and reduce the dissolution of internal transition metals.
In some embodiments of the present application, the general formula Na d R e Q f F g The compounds shown include Na 2 CoPO 4 F、Na 2 NiPO 4 F、Na 2 MnPO 4 F、Na 2 CrPO 4 F、NaVPO 4 F、Na 3 V 2 (PO 4 ) 2 F 3 、Na 3 VCo(PO 4 ) 2 F 3 、Na 3 VNi(PO 4 ) 2 F 3 、Na 3 VMn(PO 4 ) 2 F 3 、Na 3 VCr(PO 4 ) 2 F 3 Or Na (or) 3 GaV(PO 4 ) 2 F 3 。
In this embodiment, the coating layer completely coats the surface of the core. Thus, the area of the core material which is not coated can be prevented from becoming water and CO 2 And the like, the storage stability of the inner core and the stability of slurry in the pulping process are better improved, and the circulation stability and the safety performance of the inner core are further ensured.
In this embodiment, the mass of the material of the coating layer is 0.1wt% to 20wt% of the mass of the core. This helps to form a coating layer of a proper thickness, effectively suppressing water and CO in the air 2 Erosion to the core ensures good storability or processing convenience of the core material.
In the embodiment of the application, the thickness of the coating layer is 0.5nm-200nm. The coating layer with proper thickness can effectively improve the stability of the core material in the air, and the specific capacity exertion of the core material is not obviously influenced.
In some embodiments of the present application, a diffusion layer is further provided between the inner core and the cladding layer, wherein the diffusion layer comprises a material of the inner core and a material of the cladding layer. The presence of the diffusion layer may improve the bond tightness between the core and the cladding layer.
A second aspect of the embodiments of the present application provides a method for preparing a composite positive electrode material for a sodium battery, including:
constructing a coating layer on the surface of the layered sodium positive electrode active material to obtain a composite positive electrode material; wherein the material of the coating layer is a high-voltage type sodium active material with higher sodium removal potential than the layered sodium positive electrode active material, and the high-voltage type sodium active material comprises a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 At least one of N; wherein 0 is<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga, ge, as, se, in, sn, sb, te, tl, bi, and G comprises one or more of Li, mg, zn, ru, ir; 0 <d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R represents a metal element, Q represents a polyanion group, and F represents a fluorine element.
The preparation method of the composite positive electrode material is simple in flow, easy to operate and suitable for large-scale production.
The third aspect of the embodiment of the application also provides a positive electrode plate, which comprises the sodium battery composite positive electrode material according to the first aspect of the embodiment of the application.
The fourth aspect of the embodiment of the application also provides a sodium secondary battery, which comprises the sodium battery composite positive electrode material of the first aspect of the embodiment of the application. The sodium secondary battery has good cycle performance and safety performance, and maintains high specific capacity characteristics.
A fifth aspect of the embodiments of the present application provides an electronic device, which includes the sodium secondary battery according to the fourth aspect of the present application. This electronic equipment is through adopting the sodium secondary cell power supply that this application embodiment provided, can promote the use experience and the market competition of product.
A sixth aspect of the embodiments of the present application provides an energy storage system, which includes the sodium secondary battery according to the fourth aspect of the embodiments of the present application. The sodium secondary battery adopted by the energy storage system has good circulation stability and safety performance.
Drawings
Fig. 1A is a schematic structural diagram of a sodium battery composite positive electrode material according to an embodiment of the present application.
Fig. 1B is a schematic structural diagram of another sodium battery composite positive electrode material according to an embodiment of the present disclosure.
Fig. 2 is a schematic structural view of a sodium secondary battery provided in an embodiment of the present application.
Fig. 3 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
Fig. 4 is a schematic structural diagram of an energy storage system according to an embodiment of the present application.
Detailed Description
Embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application.
Fig. 1A is a schematic structural diagram of a composite positive electrode material 100 for sodium battery according to an embodiment of the present application, where the composite positive electrode material 100 includes a core 10 and a coating layer 20 coated on the core 10, the core 10 includes a layered sodium positive electrode active material, the material of the coating layer 20 is a high voltage type sodium active material with a higher sodium removal potential than the core, and the high voltage type sodium active material includes a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 At least one of N; wherein 0 is<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga (gallium), ge (germanium), as (arsenic), se (selenium), in (indium), sn (tin), sb (antimony), te (tellurium), tl (thallium) and Bi (bismuth), and G comprises one or more of Li (lithium), mg (magnesium), zn (zinc), ru (ruthenium) and Ir (iridium); 0 <d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R represents a metal element, Q represents a polyanion group, and F represents a fluorine element.
The term "layered sodium positive electrode active material" in this application refers to a layered positive electrode active material that can perform energy storage by deintercalation/intercalation of sodium ions, or a layered positive electrode active material that can reversibly deintercalate and intercalate sodium ions. "high voltage type sodium active material" refers to a sodium active material having a higher sodium removal potential than the core material. It will be appreciated that the material of the cladding layer 20 is a different sodium electroactive material than the material of the core 10; the material of the coating has sodium electrochemical activity and a higher sodium removal potential than the core 10. Wherein the material of the coating layer 20 may include at least one compound of the general formula Na m E a J b G c O n The compound shown in the specification or comprises at least one compound shown as a general formula Na d R e Q f F g The compounds shown, or include Na 3 V(PO 3 ) 3 N, or a combination of two or more of the foregoing 3-class materials, and the like. In addition, na m E a J b G c O n 、Na d R e Q f F g 、Na 3 V(PO 3 ) 3 Na in N is sodium element, na m E a J b G c O n Wherein O is oxygen element, na 3 V(PO 3 ) 3 N is a specific compound, wherein V is vanadium element, N is nitrogen element, and P is phosphorus element.
According to the sodium battery composite positive electrode material 100 provided by the embodiment of the application, the coating layer 20 is arranged on the surface of the inner core 10, and the sodium-containing coating layer can be obtained by reacting the coating layer raw material with residual sodium on the surface of the inner core, so that the residual alkali on the surface of the inner core can be reduced, and the pH of the material can be reduced. The material of the coating 20 has a high sodium removal potential, good stability in humid air, and good resistance to water and CO 2 Has good defenses, can permanently protect the inner core 10, isolate the inner core material from direct contact with humid air, and prevent H from causing 2 O、CO 2 Intercalation of molecules and Na + /H + Is exchanged to continuously generate residual alkali and prolong the core materialAnd the stable storage time of the material and the material structure change and performance reduction caused by deliquescence and water absorption are prevented; in the stirring pulping process of the positive electrode slurry, the coating layer 20 also helps to stabilize the positive electrode slurry, and the problems of slurry gelation, difficult coating and the like caused by easy water absorption and deterioration due to high residual alkali content on the surface of the core material are avoided. In addition, the coating layer 20 has sodium electrochemical activity, and can perform certain Na removal/intercalation within the charge-discharge voltage window of the core material + The electrochemical reaction does not sacrifice the gram capacity of the core material or even contributes to additional gram capacity. Furthermore, the sodium removal potential of the coating layer 20 is higher than that of the inner core 10, the composite material has better structural stability under high voltage, and when the composite material is charged in a higher voltage range, the composite material can prevent transition metal ions of the inner core 10 from being dissolved out of the coating layer 20 into electrolyte, so that the structure of the inner core is stabilized, side reactions of the composite material and the electrolyte are avoided, and the cycle stability is improved.
Therefore, the coating layer 20 can improve the air stability of the core 10 material without reducing the gram capacity of the core 10 material, and endow the composite positive electrode material with good storage and processing properties, good cycle performance, high specific capacity and other electrochemical properties, thereby being beneficial to promoting the development of low-cost sodium batteries.
In this embodiment, the discharge gram capacity of the cladding 20 material does not exceed 80%, typically 50% -70%, of the discharge gram capacity of the core 10 over the operating voltage range of the core 10. Thus, the coating layer not only contributes to capacity, but also does not generate transition sodium removal, thereby being beneficial to maintaining the crystal structure stability of the coating layer, particularly being beneficial to reducing the unit cell volume change of the core material under a high voltage window, reducing the dissolution of internal transition metal and improving the circulation stability. The "operating voltage of the core" refers to a voltage range between a charge cutoff voltage and a discharge cutoff voltage of the core material. The composite positive electrode active material is generally applied to a sodium ion battery system with a charge cutoff voltage of 2.0-4.3V, and the specific charge cutoff voltage can be adjusted according to the core material.
In this embodiment, the high voltage type sodium active material has a sodium removal potential at least 0.2V higher than the sodium removal potential of the core 10. In some embodiments, the high voltage sodium active material is 0.3V higher than the sodium removal potential of the core 10, e.g., 0.3V-1V higher. Specifically, the height may be 0.32V, 0.35V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 0.95V, or the like.
In an embodiment of the present application, the high voltage type sodium active material has a sodium removal potential of 3.3V or more. Specifically, general formula Na m E a J b G c O n The sodium removal potential of the compound is above 3.3V; polyanionic sodium active material (Na d R e Q f F g The compound shown as Na 3 V(PO 3 ) 3 N) is above 3.3V, even above 3.5V.
In the present application, general formula Na m E a J b G c O n The compounds shown are high voltage oxides containing sodium and transition metal elements, wherein the compounds must contain sodium, oxygen, E and J elements, and G is optional, in some cases G. Wherein J element such as Ga, ge, as, se, in, sn, sb, te, tl, bi is a compound Na which contributes to the construction of a honeycomb structure m E a J b G c O n Is favorable for improving the sodium removal potential of the material, and further has higher air stability so as to better protect the inner core material from water and CO 2 And the like. In the presence of Li, mg, zn, ru, ir, etc. G elements, helps to excite the compound Na m E a J b G c O n And the oxidation and reduction of the medium oxygen anions can improve the sodium removal potential of the medium oxygen anions, so that the air stability of the material can be further improved.
In the embodiment of the present application, the E may include one or more of V (vanadium), cr (chromium), fe (iron), co (cobalt), ni (nickel), mn (manganese), cu (copper), and Ti (titanium). In some embodiments of the present application, the G comprises one or more of Mg, ru, ir. When G is these elements, the compound Na m E a J b G c O n The sodium removal potential of (2) is higher.
In the present application,general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 N is a polyanion compound of sodium, their sodium removal potential is higher, stability in air is higher than lamellar sodium positive electrode active material, adopt it as the cladding material of lamellar sodium positive electrode active material, can promote the air stability of the kernel, and this polyanion compound because of having sodium electrochemical activity, adopt it as cladding material, can not reduce the specific capacity of the whole composite material. Wherein, general formula Na d R e Q f F g The compounds shown contain both polyanion groups Q and fluorine (F) elements. The existence of F element can improve the sodium removal potential of the polyanion compound through the strong induction effect of fluoride ion, so that the polyanion compound has higher air stability and is convenient for protecting the core material.
General formula Na d R e Q f F g Wherein R represents a metal element, where the metal element includes, but is not limited to, a transition metal element, and/or a main group metal element, and is more commonly referred to as a transition metal element. In the present embodiment, R may be selected from one or more of V (vanadium), cr (chromium), fe (iron), co (cobalt), ni (nickel), mn (manganese), cu (copper), ti (titanium), zr (zirconium), al (aluminum), etc., but is not limited thereto. Wherein the polyanion group Q may be selected from one or more of phosphorus oxyacid radical, sulfur oxyacid radical, silicon oxyacid radical, boron oxyacid radical, and the like. In particular, the oxyacid radical of phosphorus may include PO 4 3- 、PO 3 3- 、P 2 O 7 4- 、HPO 4 2- 、H 2 PO 4 - One or more of, etc.; the oxygen-containing acid radical of sulfur may include SO 4 2- 、SO 3 2- 、HSO 4 - One or more of, etc.; the oxygen-containing acid radical of silicon may comprise SiO 4 4- 、SiO 3 2- One or more of, etc.; the oxygen-containing acid radical of boron can comprise BO 3 3- 、BO 2 - 、B 4 O 7 2- 、B 5 O 10 5- And the like.
In some embodiments of the present application, formula Na d R e Q f F g The compounds shown include in particular Na 2 CoPO 4 F、Na 2 NiPO 4 F、Na 2 MnPO 4 F、Na 2 CrPO 4 F、NaVPO 4 F、Na 3 V 2 (PO 4 ) 2 F 3 、Na 3 VCo(PO 4 ) 2 F 3 、Na 3 VNi(PO 4 ) 2 F 3 、Na 3 VMn(PO 4 ) 2 F 3 、Na 3 VCr(PO 4 ) 2 F 3 Or Na (or) 3 GaV(PO 4 ) 2 F 3 . The polyanion compounds have higher sodium removal potential and better air stability, and the sodium removal potential of the polyanion compounds is generally above 3.3V.
In the embodiment of the application, the sodium ion conductivity of the coating material at 20 ℃ is more than or equal to 10 -5 S·cm -1 . By adjusting and controlling the composition and the relative content of the elements in the coating material, a coating with good ionic conductivity can be obtained, which is beneficial to the improvement of the ionic conductivity of the whole composite positive electrode material 100 and the improvement of the multiplying power performance.
Typically, the layered sodium positive electrode active material is a transition metal oxide of sodium. In embodiments of the present application, the layered sodium positive electrode active material may be represented as Na x A y M z D u O v Wherein 0 is<x≤12，0<y≤12，0≤z≤12，0≤u≤12，0<v is less than or equal to 12.A is a variable valence transition metal element, in some embodiments a may include one or more of V (vanadium), cr (chromium), fe (iron), co (cobalt), ni (nickel), mn (manganese), cu (copper), ti (titanium). M is an element capable of substituting/doping a transition metal element, and M can comprise one or more of Li (lithium), al (aluminum), mg (magnesium), ca (calcium), K (potassium), zn (zinc), sn (tin), and the like; d includes one or more of C (carbon), P (phosphorus), si (silicon), B (boron), W (tungsten).
In an embodiment of the present application, the particle size of the layered sodium positive electrode active material is 50nm to 30 μm. The layered sodium positive electrode active material has a larger particle diameter, a specific surface area of the layered sodium positive electrode active material is not excessively large, and structural stability is high, but the particle diameter is not excessively large so as not to increase a diffusion path of sodium ions therein and deteriorate the rate performance of the layered sodium positive electrode active material. In some embodiments, the layered sodium positive electrode active material has a particle size of 500nm to 20 μm. The layered sodium positive electrode active material with proper particle size can have higher structural stability and shorter sodium ion diffusion path.
In the present embodiment, as shown in fig. 1A, the cladding layer 20 entirely covers the surface of the core 10. Thus, the uncoated area of the layered sodium positive electrode active material can be prevented from becoming water and CO 2 And the like, the storage stability of the inner core and the stability of slurry in the pulping process are better improved, and the circulation stability and the safety performance of the inner core are further ensured.
In the present embodiment, the thickness of the clad layer 20 may be 0.5nm to 200nm. The coating layer with proper thickness can effectively inhibit the water and CO in the wet air of the layered sodium positive electrode active material 2 The reaction of the core material in the air is improved, and the specific capacity of the core material is not affected by the excessive thickness of the coating layer 20, and the energy density of the sodium battery is reduced. Specifically, the thickness of the clad layer 20 may be 1nm, 2nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, etc. In some embodiments, the thickness of the cladding layer 20 may be 2nm to 100nm. In other embodiments, the thickness of the cladding layer 20 is 10nm to 80nm.
In the composite positive electrode material, the mass of the coating layer material may be 0.1wt% to 20wt% of the mass of the core material (i.e., the layered sodium positive electrode active material). This facilitates the formation of a coating layer 20 of a suitable thickness and high coating integrity, effectively suppressing water and CO in the air 2 Erosion to the inner core ensures good storability and processing convenience of the inner core material; in the circulating process of the sodium battery, the coating layer can also inhibit side reaction between the inner core and electrolyte, and ensure the capacity of the inner core to be exerted. In particular, the mass of the cladding material may be of the core material mass0.2wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt% or 18wt%, etc. In some embodiments, the mass of the cladding material is 0.5wt% to 20wt% of the mass of the core material; in other embodiments, the mass fraction is 1wt% to 15wt%.
In the present embodiment, the bulk phase of the core 10 may be doped with elements derived from the cladding layer 20. Wherein for the general formula Na m E a J b G c O n The cladding material shown, the elements that are doped into the core bulk phase include the J element, or the J element + G element, or the E element that is different from the a element in the core. For general formula Na d R e Q f F g The cladding material shown, the element that is doped into the core phase is the metallic element R, typically a transition metal element. Bulk doping helps to improve the ionic conductivity and structural stability of the core material, thereby significantly improving the rate capability and cycling stability of the composite positive electrode material 100.
In some embodiments of the present application, referring to fig. 1B, a diffusion layer 12 is further provided between the core 10 and the cladding layer 20 of the composite positive electrode material 100, and the diffusion layer 12 includes a material of the core 10 (i.e., a layered sodium positive electrode active material) and a material of the cladding layer 20. The diffusion layer 12 may be formed by interdiffusion of the core material and the cladding material, the diffusion layer 12 and the core 10 may have a continuous layered sodium positive electrode active material phase, and the diffusion layer 12 and the cladding 20 may have a continuous cladding material phase. The diffusion layer can improve the bonding tightness between the core 10 and the coating layer 20, enhance the transmission of sodium ions and electrons on the core interface, effectively restrict the dissolution of transition metal elements in the bulk phase of the sodium positive electrode active material, stabilize the lattice structure, and obviously improve the circulation stability.
In some embodiments, in the diffusion layer 12, the cladding material diffuses into the bulk phase of the core material and/or at the surface, forming J-O-A bonds or R-O-A bonds. Wherein A is a transition metal element in the core material, J is Na which is derived from the coating layer material m E a J b G c O n R is an element derived from a polymerNon-sodium metallic elements of the anionic coating material. Wherein the J element corresponds to an ion, e.g. Sn 4+ 、Sb 5+ All belong to d10 electronic structures and cannot be combined with O 2p The orbit is hybridized, so that the coordination environment of oxygen atoms in the layered sodium positive electrode active material is changed, the interaction of A-O bonds is enhanced, the stability of the lattice structure of the layered positive electrode active material can be improved, and the electrochemical performance of the composite material is improved.
In the present embodiment, the thickness of the diffusion layer 12 is primarily dependent on the coating material, the ability of the core material to interdiffuse, and in particular the ability of the coating material to diffuse into the core 10. The thickness of the diffusion layer 12 may be 0.1nm to 20nm in order to better form a tight bond between the core 10 and the cladding layer 20. Specifically, it may be 0.2nm, 0.5nm, 1nm, 1.5nm, 2nm, 5nm, 10nm, 15nm, etc. In some embodiments, the diffusion layer 12 has a thickness of 0.2nm to 10nm; in some embodiments, the diffusion layer 12 has a thickness of 0.2nm to 5nm.
The embodiment of the application also provides a preparation method of the composite anode material, which can comprise the following steps:
constructing a coating layer on the surface of the layered sodium positive electrode active material to obtain a composite positive electrode material; wherein the material of the coating layer is a high-voltage type sodium active material with higher sodium removal potential than the layered sodium positive electrode active material, and the high-voltage type sodium active material comprises a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 At least one of N; wherein 0 is<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga, ge, as, se, in, sn, sb, te, tl, bi, and G comprises one or more of Li, mg, zn, ru, ir; 0<d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R represents a metal element, Q represents a polyanion group, and F is a fluorine element.
The coating layer can be formed by mixing a layered sodium positive electrode active material with a coating layer material or a raw material for synthesizing the coating layer material. The method for constructing the coating layer includes, but is not limited to, one or more of a solid phase method, a liquid phase method and other methods. The solid phase method can be mechanical stirring method, solid phase high energy ball milling method, mechanical fusion method, etc., and the liquid phase method can be one or more of sol-gel method, hydrothermal/solvothermal coating method, coprecipitation coating method, liquid phase high energy ball milling method, coating method, spray drying coating method. Other methods may be one or more selected from atomic layer deposition, chemical vapor deposition, physical vapor deposition (e.g., magnetron sputtering, plasma sputtering, vapor deposition), microwave reaction, etc. Generally, after mixing, a high temperature sintering process is also required to promote crystallization of the clad material and enhance the bonding force with the sodium positive electrode active material.
In some embodiments of the present application, the preparation method of the composite positive electrode material may specifically include:
s01, mixing a layered sodium positive electrode active material with a coating layer raw material to obtain a first composite material; wherein the raw material of the coating layer is a high-voltage sodium active material or an element source for synthesizing the high-voltage sodium active material, and the high-voltage sodium active material comprises a compound shown as a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compound shown as Na 3 V(PO 3 ) 3 At least one of N; wherein 0 is<m≤3，0<a≤3，0<n≤3，0<b is less than or equal to 3, c is less than or equal to 0 and less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga, ge, as, se, in, sn, sb, te, tl, bi, and G comprises one or more of Li, mg, zn, ru, ir; 0<d≤4，0<e≤4，0<f≤4，0<g is less than or equal to 3, R represents a metal element, Q represents a polyanion group, and F represents a fluorine element;
s02, sintering the first composite material to obtain a composite anode material; the composite positive electrode material comprises a core and a coating layer coated on the core, wherein the core comprises a layered positive electrode active material, and the coating layer comprises the metal oxide.
In step S01, the method of coating the precursor of the coating material includes the above-mentioned in-situ reaction coating method, where the in-situ reaction coating method mainly includes mixing the raw material for synthesizing the coating material with the positive electrode active material, and performing in-situ reaction to obtain the precursor of the coating material, and at the same time, coating the positive electrode active material. The coating material precursor may be converted into a coating material after the sintering treatment in step S02. In step S01, the mixing method of the mixing may be one or more of the aforementioned solid phase method, liquid phase method, and other methods.
In some embodiments, when the coating raw material used in the step S01 is each element source of the high-voltage type sodium active material, the coating of the layered sodium positive electrode active material may be achieved while the precursor of the coating material is prepared after the mixing treatment of the step S01. The coating material precursor may be converted into a coating material after the sintering treatment in step S02.
For the general formula Na d R e Q f F g The coating materials (i.e., the source materials required for synthesizing the coating materials) include, in particular, sodium source, metal R source (i.e., the source material containing metal element R), polyanion group source, and fluorine source. Wherein, the sodium source can be one or more of hydroxide, carbonate, nitrate, oxalate, acetate, sulfate, phosphate and fluoride salt of Na. Similarly, the metal R source may specifically include one or more of oxides, hydroxides, carbonates, nitrates, oxalates, acetates, sulfates, phosphates, fluorine-containing salts of V, fe, cr, mn, co, ni, cu, ti, zr, al, etc. The fluorine source may be NH 4 F、NH 4 HF 2 One or more of NaF, etc. The source of the polyanionic group (Q) includes one or more of the source of the oxyacid of P, the source of the oxyacid of S, the source of the oxyacid of Si, the source of the oxyacid of B, etc., wherein the source of the oxyacid of P may be selected from NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、(NH 4 ) 3 PO 4 、H 3 PO 4 、NH 4 H 2 PO 3 、(NH 4 ) 2 HPO 3 、H 3 PO 3 、(NH 4 ) 4 P 2 O 7 One or more of the following; the oxyacid radical of S may include Na 2 SO 4 、NaHSO 4 、Na 2 SO 3 One or more of the following; the source of the oxyacid radical of Si is selected from Na 2 O.nSiO 2 、H 2 SiO 3 、C 8 H 20 O 4 One or more of Si (TEOS); b is an oxyacid source selected from H 3 BO 3 、HBO 2 、Na 2 B 4 O 7 One or more of (a) and (b); the source of the oxyacid of tungsten is selected from WO 3 、H 2 WO 4 、(NH 4 ) 2 WO 4 One or more of the following. In addition, synthesize Na 3 V(PO 3 ) 3 N is a raw material source and has a general formula of Na d R e Q f F g Similar polyanionic compounds of (a) may include a sodium source, a vanadium source, a phosphorus source, and a nitrogen source. Wherein, these raw material sources may be one with two or one with more, for example, the sodium source and the phosphorus source may be the same material.
For the general formula Na m E a J b G c O n The coating material of (a) comprises a sodium source, an element E source, a J source and an optional G element source. E. The raw material of J, G element may be selected from oxides, hydroxides, carbonates, nitrates, oxalates, acetates, sulfates, phosphates, fluorine-containing salts, etc. of the corresponding element, and preferably contains oxygen. In addition, for the general formula Na m E a J b G c O n The coating material of (a) can be prepared into a precursor (such as hydroxide) by adopting a sol-gel method, and specifically comprises the following steps: adding a lithium source, a raw material of an element E, a raw material of an element J and an optional raw material of an element G into a solvent, reacting under stirring, and evaporating the solvent to dryness to form a coating layer precursor material on the surface of the layered sodium positive electrode active material. Wherein the stirring reaction time can be 20-60min. The solvent used may include one or more of water, ethanol, acetone, etc. Evaporating to dryness The heating temperature adopted by the agent is 60-100 ℃.
In some embodiments of the present application, in step S01, if the raw material of the coating layer is each element source for synthesizing the high voltage type sodium active material, the element source used may not contain a sodium source, and the sodium element in the finally obtained coating layer may be derived from the layered sodium positive electrode active material, for example, specifically derived from the residual sodium on the surface thereof, that is, the coating layer may be obtained by consuming the residual sodium reaction on the surface of the core.
In some embodiments, the mixing of step S01 may be performed using a solid phase method. The solid phase method may be specifically a mechanical stirring method, a high-energy ball milling method, a mechanical fusion method, or the like. Wherein the solid phase mixing time in the solid phase method is 2h-24h, and further can be 10-24h. In a specific embodiment, the curing and mixing can be realized by a ball milling method, so that the core-shell composite material can be conveniently prepared. The rotation speed of ball milling can be 100-700r/min, for example, 200r/min, 300r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min, etc. In some embodiments, the rotational speed of the ball mill may be 400-700r/min.
In other embodiments, when the coating layer raw material used in step S01 is a desired high voltage type sodium active material, the high voltage type sodium active material may be coated on the surface of the layered sodium positive electrode active material after the mixing treatment in step S01.
When the coating layer raw material used in the step S01 is a high-voltage type sodium active material, the bonding force between the inner core layered sodium positive electrode active material and the coating layer can be improved through the sintering treatment of the step S02; when the raw material of the coating layer used in the step S01 is a raw material source for synthesizing the high-voltage sodium active material, the sintering treatment in the step S02 can achieve the tight coating of the core while obtaining the coating layer material, i.e., the high-voltage sodium active material.
In some embodiments, the first composite material is sintered, and a diffusion layer may be formed between the core and the cladding layer, the diffusion layer including a core material and a cladding layer material. The sintering treatment can not only improve the binding force between the inner core layered sodium positive electrode active material and the coating layer, but also promote the inner core and the coating layer to mutually diffuse to form a diffusion layer, thereby enhancing the transmission of sodium ions and electrons on the interface of the inner core layered sodium positive electrode active material and the coating layer.
The sintering treatment in step S02 may be performed in an atmosphere of oxygen, air, nitrogen, argon, helium, or the like. In order to ensure that the coating layer forms a required crystal phase structure, ensure the bonding tightness of the inner core and the coating layer, and realize the uniform and continuous thickness of the coating layer, the embodiment of the application sets the sintering temperature and the heat preservation time in the sintering process, wherein the sintering temperature in the sintering process can be 200-900 ℃, and the sintering heat preservation time can be 0.5-12 h. Illustratively, the sintering temperature may specifically be 250, 300, 400, 500, 600, 650, 700, 800, 850 ℃, etc., and in some embodiments, the sintering temperature may be 300-700 ℃. The sintering heat preservation time can be 1h, 2h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, etc. In addition, the rate of temperature rise during the sintering process may be 0.5-20 ℃/min, such as 1, 2, 3, 5, 8, 10, 15 ℃/min, etc. In some embodiments, the ramp rate may be 0.5-5 ℃/min. This avoids the occurrence of large stresses at the interface between the phases due to too high a rate of temperature rise.
And after sintering, naturally cooling and collecting powder to obtain the composite anode material. In some embodiments, the powder collected after sintering may also be subjected to a crushing and refining treatment to obtain a composite positive electrode material of a desired particle size.
The preparation method of the composite positive electrode material provided by the embodiment of the application has the advantages of low raw material cost, simple flow, easiness in operation and suitability for large-scale production.
The embodiment of the application also provides a positive electrode plate for the sodium battery, which comprises the sodium battery composite positive electrode material. In some embodiments of the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode material layer disposed on the positive electrode current collector, where the positive electrode material layer includes the above-mentioned composite positive electrode material according to the embodiments of the present application. The positive electrode material layer may further include a binder and a conductive agent. In some embodiments, a positive electrode active material layer may also be included therein that is different from other positive electrode active materials.
The positive current collector is a common choice in the sodium battery field and may be, for example, aluminum foil, carbon coated aluminum foil, aluminized polymer film. The binder may specifically include, but is not limited to, one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyimide (PI), polyacrylic acid (PAA), polyacrylate, polyacrylamide (PAM), carboxymethyl cellulose (CMC), styrene Butadiene Rubber (SBR), sodium alginate, and the like. The conductive agent may specifically include, but is not limited to, one or more of acetylene black, ketjen black, super P conductive carbon black, graphite, graphene, carbon nanotubes, carbon fibers, amorphous carbon, and the like.
The preparation method of the positive electrode plate can comprise the following steps: mixing the composite positive electrode material, the conductive agent and the binder, which are implemented by the application, with a solvent to prepare positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, drying and rolling to obtain a positive electrode plate.
Referring to fig. 2, an embodiment of the present application also provides a sodium secondary battery 200 including the above-described positive electrode tab. The sodium secondary battery 200 comprises a positive electrode 201, a negative electrode 202, a diaphragm 203 arranged between the positive electrode 201 and the negative electrode 202, an electrolyte 204 and corresponding communication accessories and circuits, wherein the positive electrode 201 comprises the positive electrode plate in the embodiment of the application.
In the charging process of the sodium secondary battery, sodium ions are separated from the positive electrode 201, pass through the electrolyte 204 and the diaphragm 203 and migrate to the negative electrode 202 under the action of an external circuit, meanwhile electrons flow from the positive electrode to the negative electrode through the external circuit, and electric energy is stored; in the discharging process, contrary to charging, sodium ions are separated from the negative electrode 202 and returned to the positive electrode 201 through the electrolyte 204 and the diaphragm 203, and meanwhile electrons migrate from the negative electrode to the positive electrode through an external circuit, and electric energy is released to the outside. The sodium secondary battery uses the composite positive electrode material 100, and has good cycle stability, safety performance and rate capability in the working voltage range.
The anode 202 may include an anode current collector and an anode material layer disposed on the anode current collector, the anode material layer including an anode active material, a binder, and optionally a conductive agent. The negative electrode current collector comprises, but is not limited to, a metal foil, an alloy foil or a metal plating film, and the surface of the negative electrode current collector can be etched or roughened to form a secondary structure so as to be in effective contact with the negative electrode material layer. Exemplary metal foils may be copper foil, carbon coated copper foil, or copper coated film, and exemplary alloy foils may be stainless steel foil, copper alloy foil, and the like. Wherein the negative electrode active material includes, but is not limited to, one or more of a carbon-based material, a silicon-based material, a tin-based material, and a phosphorus-based material. Wherein, the carbon-based material can comprise non-graphitized carbon (soft carbon, hard carbon, mesophase carbon microsphere, etc.), graphite (such as natural graphite, artificial graphite); the silicon-based material may include one or more of elemental silicon, silicon-based alloys, silicon oxides, silicon-carbon composites, and the like; the tin-based material may include one or more of elemental tin, tin alloys, tin oxides, tin carbon composites, and the like; the phosphorus-based material may include elemental phosphorus (e.g., black phosphorus), phosphorus-carbon composites, and the like. The separator 203 may be a polymer separator, a nonwoven fabric, etc., including but not limited to a single layer PP (polypropylene), a single layer PE (polyethylene), a double layer PP/PE, a double layer PP/PP, and a triple layer PP/PE/PP, etc. Electrolyte 204 includes a lithium salt and a non-aqueous organic solvent, which may include one or more of carbonate solvents, carboxylate solvents, ether solvents.
The sodium secondary battery of the embodiment of the application can be used for terminal consumer products such as mobile phones, tablet computers, mobile power supplies, portable computers, notebook computers, digital cameras and other wearable electronic equipment or movable electronic equipment, such as unmanned aerial vehicles, electric bicycles, electric vehicles and other products, so that the performance of the products is improved.
The embodiment of the application also provides an electronic device, which includes the sodium secondary battery 200 provided by the embodiment of the application.
The electronic device may be an electronic product including various consumer electronic products such as a cellular phone, a tablet computer, a notebook computer, a mobile power supply, a portable device, and other wearable or mobile electronic devices, a television, a video disc player, a video recorder, a camcorder, a radio recorder, a built-up sound, a record player, a compact disc player, a home office equipment, a home electronic health care equipment, and an automobile, an energy storage device, and the like.
In some embodiments, referring to fig. 3, an electronic device 300 includes a housing 301 and electronic components (not shown in fig. 3) housed within the housing 301, and a battery 302, the battery 302 powering the electronic device 300, the battery 302 including the sodium secondary battery 200 described above in the examples of the present application. The case 301 may include a front cover assembled at a front side of the terminal and a rear case assembled at a rear side, and the battery 302 may be fixed inside the rear case.
The electronic equipment provided by the embodiment of the application can meet the requirements of various electronic products on good thermal stability, long cycle life and high energy density of the battery by adopting the composite positive electrode material provided by the embodiment of the application as the positive electrode active material of the battery, and the use experience and market competitiveness of the electronic products are improved.
Referring to fig. 4, the embodiment of the present application further provides an energy storage system 400, where the energy storage system 400 includes a battery pack 401 and a battery management system 402 electrically connected to the battery pack 401, and the battery pack 401 includes the sodium secondary battery 200 provided in the embodiment of the present application.
In this application, "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. In this application, "at least one" means one or more; "plurality" means two or more (i.e., greater than or equal to two). The meaning of "at least one", "a plurality of" is similar thereto.
The embodiments of the present application are further described below in terms of a number of examples.
Example 1
The preparation of the sodium battery composite positive electrode material comprises the following steps:
Providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (average particle size of 3-10 μm), 100g of the core material was mixed with 0.36g of antimony oxide (Sb 2 O 3 ) Powder, 1.25g of nickel acetate tetrahydrate (Ni (CH) 3 COO) 2 ·4H 2 O) mixing, ball milling for 10 hours at a rotating speed of 300rpm, and placing the ball-milled materials into a tube furnace for sintering under the following conditions: raising the temperature from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat and sintering for 3h at the temperature; and naturally cooling to room temperature to obtain the composite anode material. The composite positive electrode material comprises NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An inner core, and Na formed on the surface of the inner core m Ni 2/3 Sb 1/3 O 2 The coating layer, m is between 0.5 and 1.0. The composite positive electrode material can be named as NaNi 1/3 Fe 1/3 Mn 1/3 O 2 @Na m Ni 2/3 Sb 1/3 O 2 . Wherein, the thickness of the coating layer is 10nm, and the mass of the coating layer accounts for 1.0% of the mass of the core.
Preparation of sodium secondary battery:
the composite positive electrode material of example 1 was mixed with a conductive agent Super P, a binder PVDF according to 92:4:4, mixing the materials according to the mass ratio, adding a proper amount of N-methyl pyrrolidone (NMP), and grinding uniformly to obtain anode slurry; the sizing agent is evenly coated on aluminum foil, and the pole piece is obtained after drying and rolling. And the pole piece is taken as an anode, the metal sodium piece is taken as a cathode, and the button cell is assembled in a glove box protected by argon. The button cell can be subsequently tested for electrochemical performance.
Example 2
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 100g of the core material was mixed with 0.65g of tin oxide (SnO) 2 ) Powder, 0.54g of nickel acetate tetrahydrate (Ni (CH) 3 COO) 2 ·4H 2 O) mixing, ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain a composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 1.
The composite positive electrode material obtained in example 2 includes NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Cores and tables formed in coresNa of face m Ni 1/3 Sn 2/3 O 2 Coating layer, the composite positive electrode material is named as NaNi 1/3 Fe 1/3 Mn 1/3 O 2 @Na m Ni 1/3 Sn 2/3 O 2 Wherein m is between 0.5 and 1.0. Wherein, the thickness of the coating layer is 10nm, and the mass of the coating layer accounts for 1.0% of the mass of the core.
Example 3
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 100g of the core material was mixed with 1g of Na (same as in example 1) 0.67 Ni 1/3 As 2/3 O 2 Mixing, ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain a composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 1.
The composite positive electrode material prepared in example 3 includes NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Inner core and Na formed on surface of inner core m Ni 1/3 As 2/3 O 2 Coating layer, the composite positive electrode material is named as NaNi 1/3 Fe 1/3 Mn 1/3 O 2 @Na m Ni 1/3 As 2/3 O 2 M is between 0.5 and 1.0. Wherein the thickness of the coating layer is 8nm.
Example 4
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaAl 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 (average particle diameter of 3-10 μm), 100g of the core material was mixed with 0.32g of copper oxide (CuO) powder, 1.34g of tellurium oxide (TeO) 2 ) Mixing, ball milling for 8 hours at the rotating speed of 250rpm, and sintering the ball-milled materials in a tube furnace under the following sintering conditions: raising the temperature from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat and sintering for 3h at the temperature; and naturally cooling to room temperature to obtain the composite anode material.
The composite positive electrode material prepared in example 4 includes NaAl 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 A core formed on the surface of Na m Cu 1/3 Te 2/3 O 2 And a coating layer. The composite positive electrode material is recorded as NaAl 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 @Na m Cu 1/3 Te 2/3 O 2 M is between 0.5 and 1.0. Wherein the thickness of the coating layer is 15nm, and the mass of the coating layer accounts for about 2.0% of the mass of the core material.
Example 5
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaZn 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 (average particle diameter of 3-8 μm), 100g of the core material was mixed with 0.16g of copper oxide (CuO) powder, 0.67g of tellurium oxide (TeO) 2 ) Mixing, ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain a composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 4.
The composite positive electrode material prepared in example 5 includes NaZn 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 An inner core, and Na formed on the surface of the inner core m Cu 1/3 Te 2/3 O 2 And a coating layer. The composite positive electrode material can be named as NaZn 0.05 Ni 0.35 Fe 0.2 Mn 0.4 O 2 @Na m Cu 1/3 Te 2/ 3 O 2 M is between 0.5 and 1.0. Wherein the thickness of the coating layer is 14nm, and the mass of the coating layer accounts for about 1.0% of the mass of the core.
Example 6
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaCa 0.02 Ni 0.33 Fe 0.33 Mn 0.33 O 2 (single crystal, average particle diameter of 5-7 μm), 100g of the core material and 1g of Na 0.8 Mg 0.1 Ni 1/3 Bi 2/3 O 2 Mixing, ball milling for 10 hours at a rotating speed of 300rpm, and sintering the ball-milled materials in a tube furnace under the following sintering conditions: raising the temperature from room temperature to a sintering temperature of 700 ℃ at a heating rate of 3 ℃/min, and preserving heat and sintering for 4 hours at the temperature; and naturally cooling to room temperature to obtain the composite anode material.
The composite positive electrode material prepared in example 6 includes NaCa 0.02 Ni 0.33 Fe 0.33 Mn 0.33 O 2 An inner core, and Na formed on the surface of the inner core m Mg 0.1 Ni 1/3 Bi 2/3 O 2 The coating layer, m is between 0.5 and 1.0. Wherein, the thickness of the coating layer is 10nm, and the mass of the coating layer accounts for 1.0% of the mass of the core.
Example 7
The preparation of the composite positive electrode material comprises the following steps:
providing core material-layered sodium positive electrode active material Na 2 Mn 3 O 7 (single crystal, average particle diameter of 5-7 μm), 100g of the core material and 1g of Na 0.67 Li 0.1 Ni 1/3 Bi 2/3 O 2 Mixing (average particle size is not more than 500 nm), ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain a composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 6.
The composite positive electrode material prepared in example 7 includes Na 2 Mn 3 O 7 A core formed on the surface of Na m Li 0.1 Ni 1/ 3 Bi 2/3 O 2 The coating layer, m is between 0.5 and 1.0. The composite positive electrode material was designated as Na 2 Mn 3 O 7 @Na m Li 0.1 Ni 1/3 Bi 2/3 O 2 . Wherein the thickness of the coating layer is 9nm.
Example 8
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 100g of the core material was mixed with 1.5g of Na (same as in example 1) 0.67 Ca 0.05 Ni 1/3 Ge 2/3 O 2 Mixing, ball milling for 5 hours at a rotating speed of 200rpm, and placing the ball-milled materials into a tube furnace for sintering under the following conditions: raising the temperature from room temperature to the sintering temperature of 600 ℃ at the heating rate of 5 ℃/min, and preserving the temperature at the temperature for sintering for 3 hours; and naturally cooling to room temperature to obtain the composite anode material.
Wherein the composite positive electrode material prepared in example 8 comprises NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Inner core and Na formed on surface of inner core 0.67 Ca 0.05 Ni 1/3 Ge 2/3 O 2 And a coating layer. Wherein, the thickness of the coating layer is 9nm, and the mass of the coating layer accounts for 1.5% of the mass of the core.
Example 9
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (average particle diameter of 3-10 μm), 100g of the core material and 1g of Na 3 (VPO 4 ) 2 F 3 (average grain diameter is not more than 500 nm), ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain the composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 1.
The composite cathode material prepared in example 9 includes NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An inner core, and Na formed on the surface of the inner core 3 V 2 (PO 4 ) 2 And F, coating. The composite positive electrode material was designated as NaNi 1/3 Fe 1/3 Mn 1/3 O 2 @Na 3 (VPO 4 ) 2 F 3 . Wherein the thickness of the coating layer is 5nm.
Example 10
The preparation of the composite positive electrode material comprises the following steps:
providing a core material, namely a layered sodium positive electrode active material NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (average particle diameter of 3-10 μm), 100g of the core material and 1g of Na 2 CoPO 4 F (average particle size not more than 500 nm) mixing, ball milling, sintering in a tube furnace, and naturally cooling to room temperature to obtain the composite anode material; wherein, the conditions of ball milling and sintering are the same as in example 1.
The composite positive electrode material prepared in example 10 includes NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An inner core, and Na formed on the surface of the inner core 2 MnPO 4 And F, coating. The composite positive electrode material was designated as NaNi 1/3 Fe 1/3 Mn 1/3 O 2 @Na 2 CoPO 4 F. Wherein the thickness of the coating layer is 6nm.
To highlight the beneficial effects of the embodiments of the present application, the following comparative examples are specifically provided.
Comparative example 1
Directly taking uncoated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 As a positive electrode active material, a button sodium battery was assembled in the same manner as in example 1.
In order to measure the air stability of the composite positive electrode material provided by the application, the composite positive electrode material of each embodiment is tested and stored for 7 days in an environment with the humidity of 10%, and whether the material is deliquescent and absorbs water is observed; the composite positive electrode materials were prepared into positive electrode pastes in the manner described in example 1, and the time required for gelation of the positive electrode pastes under an environment having a humidity of 10% was measured, and the results are summarized in table 1 below.
In addition, table 1 summarizes the sodium removal potential of the core material and the sodium removal potential of the cladding material in the composite material of the examples of the present application. Where both of these are sodium removal potentials tested on separate materials, not on composite materials.
To further support the benefits of the examples herein, the assembled button cell of each of the above examples and comparative examples was subjected to the following electrochemical performance tests: charging and discharging each button cell at 25 ℃ with current of 0.5C multiplying power, wherein the voltage range is 2.0-4.1V, and recording the discharge capacity under each cycle, wherein the first-cycle discharge specific capacity is equal to the ratio of the first discharge capacity of the button cell to the mass of the positive electrode active material of the button cell; the capacity retention after 50 cycles is equal to the ratio of the discharge capacity after 50 cycles to the first discharge capacity. The correlation results are summarized in Table 1.
Table 1 summary of the results associated with each example and comparative example
As can be seen from table 1, compared with comparative example 1, the gelation time of the positive electrode slurries of examples 1 to 10 is all prolonged, and the improvement effect of the coating layer on the air stability of the core material is reflected; in addition, the capacity of the first-turn discharge gram and the capacity retention rate after a certain number of turns of circulation of the button cell prepared from the composite material with the coating layer are increased, so that the improvement of air stability of the active material coating layer can be realized on the premise of not sacrificing electrochemical performance.
Claims (17)
1. The composite positive electrode material of the sodium battery is characterized by comprising an inner core and a coating layer coated on the inner core, wherein the inner core comprises a layered sodium positive electrode active material, the material of the coating layer is a high-voltage type sodium active material with sodium removal potential higher than that of the inner core, and the high-voltage type sodium active material comprises a general formula Na m E a J b G c O n The compound shown in the general formula Na d R e Q f F g The compounds and Na 3 V(PO 3 ) 3 At least one of N;
wherein 0<m is less than or equal to 3,0< a is less than or equal to 3,0< n is less than or equal to 3,0< b is less than or equal to 3,0< c is less than or equal to 3, E is a variable valence transition metal element, J comprises one or more of Ga, ge, as, se, in, sn, sb, te, tl, bi, and G comprises one or more of Li, mg, zn, ru, ir;
0<d.ltoreq.4, 0.ltoreq.e.ltoreq.4, 0.ltoreq.f.ltoreq.4, 0.ltoreq.g.ltoreq.3, R represents a metal element, Q represents a polyanion group, and F represents a fluorine element.
2. The sodium battery composite positive electrode material of claim 1, wherein the high voltage type sodium active material has a sodium removal potential at least 0.2V higher than the inner core.
3. The sodium battery composite positive electrode material according to claim 1 or 2, wherein the high-voltage type sodium active material has a sodium removal potential of 3.3V or more.
4. A sodium battery composite positive electrode material according to any one of claims 1 to 3, wherein E comprises one or more of V, cr, fe, co, ni, mn, cu, ti.
5. A sodium battery composite positive electrode material according to any one of claims 1 to 3, wherein R is selected from one or more of V, fe, cr, mn, co, ni, cu, ti, zr, al; and Q is one or more selected from phosphorus oxyacid radical, sulfur oxyacid radical, silicon oxyacid radical and boron oxyacid radical.
6. The sodium battery composite positive electrode material according to claim 5, wherein the general formula Na d R e Q f F g The compounds shown include Na 2 CoPO 4 F、Na 2 NiPO 4 F、Na 2 MnPO 4 F、Na 2 CrPO 4 F、NaVPO 4 F、Na 3 V 2 (PO 4 ) 2 F 3 、Na 3 VCo(PO 4 ) 2 F 3 、Na 3 VNi(PO 4 ) 2 F 3 、Na 3 VMn(PO 4 ) 2 F 3 、Na 3 VCr(PO 4 ) 2 F 3 Or Na (or) 3 GaV(PO 4 ) 2 F 3 。
7. The sodium battery composite positive electrode material according to any one of claims 1 to 6, wherein the layered sodium positive electrode active material is represented by Na x A y M z D u O v Wherein 0 is<x≤12，0<y≤12，0≤z≤12，0≤u≤12，0<v is less than or equal to 12, A is a variable valence transition metal element, M comprises one or more of Li, al, mg, ca, K, zn, sn, and D comprises one or more of C, P, si, B, W.
8. The sodium battery composite positive electrode material of claim 7, wherein a comprises one or more of V, cr, fe, co, ni, mn, cu, ti.
9. The sodium battery composite positive electrode material according to any one of claims 1 to 8, wherein the coating layer completely coats the surface of the core.
10. The sodium battery composite positive electrode material according to any one of claims 1 to 9, wherein the thickness of the coating layer is 0.5nm to 200nm.
11. A sodium battery composite positive electrode material according to any one of claims 1 to 10, wherein the mass of the coating layer is 0.1wt% to 20wt% of the mass of the core.
12. A sodium battery composite positive electrode material according to any one of claims 1 to 11, wherein the bulk phase of the core is doped with an element derived from the coating layer.
13. A sodium battery composite positive electrode material according to any one of claims 1 to 12, wherein a diffusion layer is further provided between the core and the coating layer, the diffusion layer comprising the material of the core and the material of the coating layer.
14. A positive electrode sheet, characterized in that it comprises the sodium battery composite positive electrode material according to any one of claims 1 to 13.
15. A sodium secondary battery comprising the positive electrode sheet according to claim 14.
16. An electronic device comprising the sodium secondary battery according to claim 15.
17. An energy storage system comprising the sodium secondary battery of claim 15.
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| CN202211166710.2A CN117810379A (en) | 2022-09-23 | 2022-09-23 | Sodium battery composite positive electrode material and application thereof |
| PCT/CN2023/120159 WO2024061289A1 (en) | 2022-09-23 | 2023-09-20 | Composite positive electrode material of sodium battery and use thereof |
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| CN110277540B (en) * | 2018-03-14 | 2020-08-04 | 中国科学院物理研究所 | Core-shell structure sodium ion battery positive electrode material and preparation method and application thereof |
| CN114361415A (en) * | 2021-12-29 | 2022-04-15 | 浙江美达瑞新材料科技有限公司 | Sodium ion battery anode material with multi-core type core-shell structure and preparation method thereof |
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| CN114678509B (en) * | 2022-04-15 | 2023-09-19 | 中国科学院化学研究所 | Sodium ion battery layered positive electrode material coated with oxyfluoride in situ and preparation method thereof |
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