WO2022267550A1 - 正极活性材料、电化学装置与电子设备 - Google Patents
正极活性材料、电化学装置与电子设备 Download PDFInfo
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- WO2022267550A1 WO2022267550A1 PCT/CN2022/079658 CN2022079658W WO2022267550A1 WO 2022267550 A1 WO2022267550 A1 WO 2022267550A1 CN 2022079658 W CN2022079658 W CN 2022079658W WO 2022267550 A1 WO2022267550 A1 WO 2022267550A1
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- positive electrode
- electrode active
- active material
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- carbon
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of secondary batteries, in particular to a positive electrode active material, an electrochemical device and an electronic device.
- Lithium-ion batteries have been widely used as an important new energy storage device in recent years due to their high energy density and good cycle performance.
- the cost of batteries has always been high, and at the same time they are facing serious problems such as the depletion of related resources, so it is necessary to develop other low-cost metal-ion secondary battery systems.
- Na-ion batteries have become a hot research direction in recent years due to their low cost, abundant sodium metal resources, and similar manufacturing processes to lithium-ion batteries.
- pyrophosphate-based cathode materials have been widely concerned due to their good cycle performance and low cost.
- direct use will affect the performance of the gram capacity of the pyrophosphate-based cathode material and its electrochemical performance is poor, which seriously hinders its large-scale application.
- the present application provides a positive electrode active material, an electrochemical device and an electronic device, which can effectively improve the conductivity of the positive electrode active material, improve the gram capacity and kinetic performance of the material, reduce the occurrence of side reactions, and improve the cycle performance of the positive electrode active material.
- the present application provides a positive electrode active material
- the positive electrode active material includes a conductive matrix material and an active material distributed on the conductive matrix material;
- the active material has a core-shell structure, and the core-shell structure consists of
- the core layer material is composed of a shell layer material, wherein the core layer material includes a phosphate-based sodium salt material, the shell layer material includes a conductive polymer, and the conductive matrix material includes a carbon material.
- the conductive polymer includes at least one of polyaniline, polypyrrole, a polymer of 3,4-ethylenedioxythiophene monomer, and polyethylene oxide.
- the positive electrode active material has at least one of the following characteristics:
- the chemical formula of the sodium phosphate salt material is Na x1 R y1 (PO 4 ) Z1 , wherein, 1 ⁇ x 1 ⁇ 3, 1 ⁇ y 1 ⁇ 2, 1 ⁇ z 1 ⁇ 3, R includes Mg, At least one of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Hf, Ta, W and Pb;
- the chemical formula of the sodium phosphate salt material is Na x2 R y2 (P 2 O 7 ) Z2 , wherein, 1 ⁇ x 2 ⁇ 7, 1 ⁇ y 2 ⁇ 3, 1 ⁇ z 2 ⁇ 4, R includes At least one of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Hf, Ta, W and Pb;
- the chemical formula of the sodium phosphate salt material is Na x3 R y3 (PO 4 ) Z3 (P 2 O 7 ) k3 , wherein, 1 ⁇ x 3 ⁇ 7, 1 ⁇ y 3 ⁇ 4, 1 ⁇ z 3 ⁇ 2, 1 ⁇ k 3 ⁇ 4, R includes Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Hf, Ta, W and at least one of Pb;
- the chemical formula of the sodium phosphate salt material is Na x4 R y4 (PO 4 ) Z4 M l1 , wherein, 1 ⁇ x 4 ⁇ 3, 1 ⁇ y 4 ⁇ 2, 1 ⁇ z 4 ⁇ 2 , 1 ⁇ l 1 ⁇ 3, R includes at least one of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Hf, Ta, W and Pb species, and M includes at least one of F, Cl, and Br.
- the phosphate-based sodium salt material includes NaFePO 4 , Na 3 V 2 (PO 4 ) 3 , Na 2 FeP 2 O 7 , Na 2 MnP 2 O 7 , NaCoP 2 O 7 , Na 7 V 3 (P 2 O 7 ) 4 , Na 2 FePO 4 F, Na 3 V 2 (PO 4 ) 2 F 3 , Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Co 3 (PO 4 ) At least one of 2 (P 2 O 7 ).
- the positive electrode active material has at least one of the following characteristics:
- the thickness of the shell material is 50nm ⁇ 400nm
- the mass content of the shell material in the positive electrode active material is 1% to 10%
- the mass content of the core layer material in the positive electrode active material is 90% to 99%.
- the positive electrode active material has at least one of the following characteristics:
- the carbon material includes at least one of carbon nanotubes, graphene, carbon fibers, natural graphite, and artificial graphite;
- the carbon material includes an oxygen-containing group, and the oxygen-containing group is selected from at least one of carboxyl, hydroxyl and ether groups;
- the carbon material includes oxygen-containing groups, and the mass content of oxygen atoms in the carbon material is ⁇ 0.1%;
- the conductive base material is a carbon material.
- the mass content of the conductive matrix material in the positive electrode active material is 1% to 10%.
- the positive electrode active material has at least one of the following characteristics:
- the positive electrode active material has a resistivity of 0.005 ⁇ cm to 100 ⁇ cm under a pressure of 20MPa;
- the average particle size of the positive electrode active material is 5 ⁇ m to 20 ⁇ m;
- the gram capacity of the positive electrode active material is 100mAh/g to 180mAh/g.
- the present application provides an electrochemical device, comprising a positive pole piece, a negative pole piece, a separator, and an electrolyte, wherein the positive pole piece includes the above-mentioned positive pole active material.
- the present application provides an electronic device, which includes the above-mentioned electrochemical device.
- the application provides a positive electrode active material, which is coated with a conductive polymer on the surface of the phosphate-based sodium salt material.
- the conductive polymer has high mechanical strength.
- the conductive conductive polymer structure is flexible and bendable, and its processability is good.
- the stability of the cladding layer can still be maintained when the volume of the material changes during charge and discharge without deformation.
- this coating layer can improve the conductivity of the sodium phosphate salt material to enhance its gram capacity and dynamic performance, and on the other hand, it can prevent the sodium phosphate salt material from being in direct contact with the electrolyte and reduce side reactions. Occurs, improving the cycle performance of the positive electrode active material.
- the high conductivity of the conductive matrix material can be used to further improve the conductivity of the material, so that the positive electrode active material with a conductive polymer coating structure and a conductive matrix material can be used. Higher gram capacity, better kinetic performance and cycle performance.
- FIG. 1 is a schematic structural view of a positive electrode active material provided in an embodiment of the present application.
- FIG. 2 is a schematic structural diagram of active materials in the positive electrode active material provided in the embodiment of the present application.
- 1-conductive matrix material 2-active material; 21-core material; 22-shell material.
- connection can be a fixed connection or a detachable connection, or an integrated connection, or Electrical connection; either directly or indirectly through an intermediary.
- the present application provides a positive electrode active material.
- Figure 1 is a schematic structural view of a positive electrode active material provided in the embodiment of the present application.
- the positive electrode active material includes a conductive matrix material 1 and is distributed on the conductive matrix. Active substance 2 on material 1.
- the active material 2 has a core-shell structure.
- FIG. 2 is a schematic structural diagram of the active material in the positive electrode active material provided in the embodiment of the present application.
- the core-shell structure consists of a core material 21 and a shell material 22.
- the core layer material 21 includes a sodium phosphate material
- the shell layer material 22 includes a conductive polymer
- the conductive matrix material 1 includes a carbon material.
- the conductive matrix material 1 can be used to construct a conductive network, and the active material 2 can be adhered to the surface of the conductive matrix material 1, or attached to the hole structure of the conductive matrix material 1, etc., which is not limited here.
- the active material 2 By attaching the active material 2 to the conductive matrix material 1, the high conductivity of the conductive matrix material 1 can be utilized to improve the conductivity of the positive electrode active material.
- the conductive matrix material 1 may be a carbon material, wherein the carbon material may include at least one of carbon nanotubes, graphene, carbon fibers, and natural graphite.
- the carbon material includes oxygen-containing groups, and the oxygen-containing groups are selected from at least one of carboxyl groups, hydroxyl groups and ether groups.
- the mass content of the oxygen atom in the oxygen-containing group can be ⁇ 0.1%.
- the mass content of the oxygen atom in the oxygen-containing group can be specifically 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% %, 0.7%, 0.8%, 0.9%, 1%, etc. are not limited here.
- the overpotential of the conductive matrix material 1 can be reduced, the phenomenon of poor affinity between the active material 2 and the positive electrode current collector can be improved, and the viscosity of the active material 2 and the positive electrode current collector can be improved. knot force.
- the mass content of the conductive matrix material 1 in the positive electrode active material can be 1% to 10%.
- the mass content of the conductive matrix material 1 in the positive electrode active material can be specifically 1%, 2%. , 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., are not limited here. If the mass content of the conductive matrix material 1 in the positive electrode active material is too high, there will be too many carbon materials with high specific surface area, no capacity, and low compaction density, and the battery capacity will become smaller, thereby reducing the energy density and cycle life of the battery.
- the mass content of the conductive matrix material 1 in the positive electrode active material may be 4% to 8%.
- the active material 2 on the conductive matrix material 1 has a core-shell structure
- the core-shell structure is composed of a core material 21 and a shell material 22
- the core material 21 is coated by the shell material 22
- the cladding structure can be It is fully coated or half coated
- the coating method can be solid phase coating method, liquid phase coating method or gas phase coating method, etc.
- the specific coating method can be selected according to actual needs, and is not limited here.
- the shell material 22 and the core material 21 of the active material 2 are closely connected by the Coulomb attraction of charges or by strong chemical bonds between the core material 21 and the shell material 22 .
- the composition of the core layer material 21 includes a sodium phosphate salt material
- the chemical formula of the sodium phosphate salt material includes Na x1 R y1 (PO 4 ) Z1 , Na x2 R y2 (P 2 O 7 ) Z2 , Na x3 R At least one of y3 (PO 4 ) Z3 (P 2 O 7 ) k3 , Na x4 R y4 (PO 4 ) Z4 M l1 .
- R includes at least one of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Hf, Ta, W and Pb, and M includes F , Cl, Br at least one.
- the sodium phosphate salt material can specifically be NaFePO 4 , Na 3 V 2 (PO 4 ) 3 , Na 2 FeP 2 O 7 , Na 2 MnP 2 O 7 , NaCoP 2 O 7 , Na 7 V 3 (P 2 O 7 ) 4 , Na 2 FePO 4 F, Na 3 V 2 (PO 4 ) 2 F 3 , Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Mn 3 (PO 4 ) 2 ( P 2 O 7 ), Na 4 Co 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ), Na 7 V 4 (PO 4 ) (P 2 O 7 ) 4 etc. are not limited here.
- the sodium phosphate salt material may be Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ).
- the shell material 22 used to cover the core layer material 21 includes a conductive polymer, wherein the conductive polymer may include polyaniline, polypyrrole, a polymer of 3,4-ethylenedioxythiophene monomer, polyethylene oxide at least one of the
- the positive electrode active material with conductive polymer coating structure has more excellent reversibility during charge and discharge.
- the conductive polymer shell has strong toughness and can be evenly coated on the surface of the phosphate-based sodium salt material, so that the mechanical strength of the positive electrode active material is improved, and the conductive polymer has strong conductivity, which can improve the phosphate-based sodium salt.
- the conductivity of the material thereby improving the conductivity of the positive electrode active material to enhance the gram capacity of the positive electrode active material and improve the kinetic performance.
- the conductive polymer shell can prevent the surface of the positive electrode active material from being in direct contact with the electrolyte, reduce the occurrence of side reactions, and improve the cycle performance of the positive electrode active material.
- the active material 2 is loaded on the conductive matrix material 1, and a large number of isolated active materials 2 can be connected through an externally constructed one-dimensional or two-dimensional conductive network to further improve the conductivity.
- the oxygen-containing functional groups of the conductive matrix material 1 are increased, and the oxygen-containing functional groups are used to form stronger hydrogen bonds with the shell material 22 on the surface of the active material 2 to improve the binding strength between the active material 2 and the conductive matrix material 1 .
- the mass content of the core layer material 21 in the positive electrode active material may be 90% to 99%.
- the mass content of the core layer material 21 in the positive electrode active material may specifically be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc., It is not limited here. If the mass content of the core layer material 21 in the positive electrode active material is too large, and the proportion of the conductive polymer covering the core layer material 21 is too small, the conductivity of the positive electrode active material will decrease, affecting the gram capacity and kinetic performance of the battery.
- the mass content of the core layer material 21 in the positive electrode active material is too small, and the proportion of the phosphate-based sodium salt material with good cycle performance is too small, resulting in a decrease in the cycle performance of the battery.
- the mass content of the core layer material 21 in the positive electrode active material may be 95%.
- the mass content of the shell material 22 in the positive electrode active material may be 1% to 10%.
- the mass content of the shell material 22 in the positive electrode active material may specifically be 1%, 2%, 3%, or 4%. . , 200nm, 350nm, 300nm, 350nm, 400nm, 450nm, 500nm, etc., are not limited here. If the mass content and thickness of the shell material 22 in the positive electrode active material are too high, the shell layer will be too thick, the mass proportion of the conductive polymer will be too high, and the mass proportion of the sodium phosphate salt material with good cycle performance in the core layer material 21 becomes smaller, which ultimately affects the cycle performance of the battery.
- the mass content and thickness of the shell material 22 in the positive electrode active material are too low, the conductive polymer cladding layer coated on the core layer material 21 is too thin, the conductivity of the positive electrode active material decreases, and the surface of the positive electrode active material is easy to contact with Electrolyte contact directly, the side reaction is aggravated.
- the mass content of the shell material 22 in the positive electrode active material may be 4% to 8%, and the thickness of the shell material 22 may be 100nm to 300nm.
- the average particle size of the positive electrode active material can satisfy 5 ⁇ m ⁇ Dv50 ⁇ 20 ⁇ m. 19 ⁇ m, 20 ⁇ m, etc. are not limited here. If the average particle size of the positive electrode active material is too small, agglomeration of particles of the positive electrode active material is prone to occur, and side reactions with the electrolyte are intensified. If the average particle size of the positive electrode active material is too large, the diffusion rate of active ions in the positive electrode active material will be reduced, resulting in a decrease in kinetic performance, which will affect the gram capacity of the positive electrode active material and the battery cycle performance. Optionally, the particle size of the positive electrode active material satisfies 8 ⁇ m ⁇ Dv50 ⁇ 15 ⁇ m.
- the present application provides an electrochemical device, including a positive pole piece, a negative pole piece, a separator, and an electrolyte, and the positive pole piece includes the above-mentioned positive electrode active material.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer located on the positive electrode current collector, and the positive electrode active material layer includes the positive electrode active material of the first aspect above.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector.
- the negative active material layer includes a negative active material.
- the negative electrode active material may include at least one of graphite, silicon material, silicon-oxygen material, tin material, tin-oxygen material or silicon-carbon composite material.
- the negative electrode active material layer may include a binder
- the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxy Polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, Acrylic (ester) styrene-butadiene rubber, epoxy resin or nylon is not limited here.
- the negative electrode active material layer can also include conductive materials, and the conductive materials can include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel , aluminum, silver or polyphenylene derivatives, etc., are not limited here.
- the negative electrode current collector may include, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam or a composite current collector coated with conductive metal.
- the aluminum-based current collector may include any one of aluminum foil, aluminum alloy foil and aluminum-based composite current collector.
- the aluminum-based composite current collector may include a polymer base film and aluminum foil and/or aluminum alloy foil formed on both sides of the polymer base film.
- the aluminum-based composite current collector has a "sandwich" structure, and the polymer base film is located in the middle, with aluminum foils on both sides, or aluminum alloy foils on both sides, or one side of the polymer base film. There is aluminum foil and the other side has aluminum foil.
- the polymer base film is polyamide, polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, poly Butylene terephthalate, poly-p-phenylene terephthalamide, polypropylene, polyoxymethylene, epoxy resin, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate any kind.
- the present application chooses aluminum-based composite current collectors with better ductility, which is beneficial to maintain the integrity of the electrodes during the sodium deposition/extraction process.
- the isolation film can be a variety of materials suitable for the isolation film of electrochemical energy storage devices in the field, for example, it can be a material including but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid , polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and at least one of natural fibers.
- the electrochemical device may further include an electrolyte, and the electrolyte includes an organic solvent, a sodium salt, and an additive.
- the organic solvent of the electrolytic solution according to the present application can be any organic solvent known in the prior art that can be used as a solvent for the electrolytic solution.
- the electrolyte used in the electrolytic solution according to the present application is not limited, and it may be any electrolyte known in the prior art.
- the additive of the electrolytic solution according to the present application may be any additive known in the prior art as an additive to the electrolytic solution.
- the organic solvent may include, but not limited to: ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate At least one of ester (DMC), vinylene carbonate, fluoroethylene carbonate, propylene carbonate, propyl propionate or ethyl propionate.
- EC ethylene carbonate
- PC propylene carbonate
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- ester DMC
- vinylene carbonate fluoroethylene carbonate
- propylene carbonate propyl propionate or ethyl propionate.
- the sodium salt may include at least one of organic sodium salt or inorganic sodium salt.
- the sodium salt may include, but not limited to: sodium hexafluorophosphate (NaPF 6 ), sodium tetrafluoroborate (NaBF 4 ), sodium difluorophosphate (NaPO 2 F 2 ), bistrifluoromethane Sodium sulfonyl imide NaN(CF 3 SO 2 ) 2 (NaTFSI), sodium bis(fluorosulfonyl)imide Na(N(SO 2 F) 2 )(NaFSI), sodium bisoxalate borate NaB(C 2 O 4 ) 2 (NaBOB), sodium difluorooxalate borate NaBF 2 (C 2 O 4 ) (NaDFOB) or sodium perchlorate.
- NaPF 6 sodium hexafluorophosphate
- NaBF 4 sodium tetrafluoroborate
- NaPO 2 F 2 sodium difluorophosphate
- NaTFSI sodium sulfonyl imide NaN(CF 3 SO 2 ) 2
- the electrochemical device of the present application may include, but not limited to: all kinds of primary batteries and secondary batteries.
- the battery includes at least one of a soft pack, a square aluminum case, a square steel case, a cylindrical aluminum case and a cylindrical steel case battery.
- the present application provides an electronic device, which includes the above-mentioned electrochemical device.
- the electronic equipment may include, but is not limited to: notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, heads Wearable stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, automobiles, motorcycles, Power-assisted bicycles, bicycles, lighting appliances, toys, game consoles, clocks, electric tools, flashlights, cameras, large household batteries, energy storage or sodium ion capacitors, etc. Electrochemical devices can be used to provide power to electronic devices.
- the present application also provides a method for preparing a positive electrode active material, and the method includes the following steps S10-S30.
- the average particle size of the carbon material after ultrasonic dispersion is 50nm to 20um
- the inlet temperature of the spray drying is 150°C to 250°C
- the outlet temperature of the spray drying is 80°C to 150°C.
- the positive active material is finally obtained.
- the carbon material was first put into a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 and stirred for 4 hours, washed with deionized water, filtered, put into an oven, and dried at 80°C.
- the carbon material and the high molecular conductive polymer are added into the dimethylpyrrolidone and stirred to form a uniform slurry, and the slurry is coated on the copper foil and dried to obtain the carbon material coating used.
- Under Ar atmosphere put the sodium metal into a stainless steel crucible and heat it to 200°C to make it melt completely, then add the alloy component powder into the liquid sodium metal and stir for 2 hours to ensure that the metal powder and the sodium metal liquid are evenly mixed, After cooling, the sodium metal alloy active material can be obtained.
- the sodium metal alloy active material is compounded on the surface of the carbon material coating by cold pressing to obtain the sodium metal negative electrode sheet.
- Ethylene glycol dimethyl ether (DME) was used as an organic solvent, and then fully dried sodium salt NaPF 6 was dissolved in the mixed organic solvent to prepare an electrolyte solution with a concentration of 1mol/L.
- the above-mentioned positive electrode sheet, separator, and negative electrode sheet are stacked in order, so that the separator is between the positive and negative electrode sheets to play the role of isolation, and the above-mentioned electrolyte is added to assemble a button battery.
- Examples 1-22 and Comparative Examples 1-7 were prepared according to the above method, and the specific parameters are shown in Table 1.
- Resistivity of the positive electrode active material the positive electrode active material powder was tested with a powder resistance tester under a pressure of 20 MPa.
- the batteries prepared in Examples and Comparative Examples were charged to 4V at a rate of 0.1C, discharged to 1V at a rate of 0.1C, and a full charge and discharge test was performed to obtain the discharge capacity as the gram capacity of the material.
- the positive electrode active materials with different compositions have slight differences in the gram capacity of the prepared batteries and the number of cycles of the batteries.
- the positive electrode active material is Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ).
- the mass content of the shell material in the positive electrode active material is too low, the conductive polymer coating layer coated on the core layer material is too thin, the conductivity of the positive electrode active material decreases, and the surface of the positive electrode active material is easy to contact with the electrolyte. Direct contact will intensify side effects.
- the mass content of the shell material in the positive electrode active material is 4% to 8%.
- the mass content of the conductive matrix material in the positive electrode active material is in the range of 1% to 10%, the service life of the battery is long. If the mass content of the conductive matrix material in the positive electrode active material is too high, there will be too many carbon materials with high specific surface area, no capacity, and low compaction density, and the battery capacity will decrease, resulting in a decrease in battery energy density and cycle life. If the mass content of the conductive matrix material in the positive electrode active material is too low, it will be difficult to form an effective conductive network between the active materials, the battery conduction rate will decrease, and the gram capacity of the active material will be difficult to exert, thereby reducing the battery life.
- the mass content of the conductive matrix material in the positive electrode active material is 4% to 8%.
- the selection of the type of conductive polymer will affect the gram capacity and cycle life of the battery.
- the shell material can be polypyrrole.
- the average particle size of the positive electrode active material is in the range of 5 ⁇ m to 20 ⁇ m, the gram capacity and cycle performance of the battery are the best.
- the average particle size of the positive electrode active material is too small, which is prone to agglomeration, and the side reaction with the electrolyte is intensified. If the average particle size of the positive electrode active material is too large, the diffusion rate of active ions in the material will be reduced, the kinetic performance will be reduced, and the gram capacity and cycle performance of the battery will be affected.
- the average particle size of the positive electrode active material satisfies 8 ⁇ m ⁇ Dv50 ⁇ 15 ⁇ m.
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Abstract
Description
Claims (10)
- 一种正极活性材料,包括导电基体材料及分布于所述导电基体材料上的活性物质;所述活性物质具有核壳结构,所述核壳结构由核层材料和壳层材料构成,其中,所述核层材料包括磷酸基钠盐材料,所述壳层材料包括导电聚合物,所述导电基体材料包括碳材料。
- 根据权利要求1所述的正极活性材料,其中,所述导电聚合物包括聚苯胺、聚吡咯、3,4-乙烯二氧噻吩单体的聚合物、聚环氧乙烷中的至少一种。
- 根据权利要求1所述的正极活性材料,其中,所述正极活性材料具有如下特征中的至少一种:(1)所述磷酸基钠盐材料的化学式为Na x1R y1(PO 4) Z1,其中,1≤x 1≤3,1≤y 1≤2,1≤z 1≤3,R包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Sn、Hf、Ta、W和Pb中的至少一种;(2)所述磷酸基钠盐材料的化学式为Na x2R y2(P 2O 7) Z2,其中,1≤x 2≤7,1≤y 2≤3,1≤z 2≤4,R包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Sn、Hf、Ta、W和Pb中的至少一种;(3)所述磷酸基钠盐材料的化学式为Na x3R y3(PO 4) Z3(P 2O 7) k3,其中,1≤x 3≤7、1≤y 3≤4、1≤z 3≤2、1≤k 3≤4,R包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Sn、Hf、Ta、W和Pb中的至少一种;(4)所述磷酸基钠盐材料的化学式为Na x4R y4(PO 4) Z4M l1,其中,1≤x 4≤3,1≤y 4≤2,1≤z 4≤2,1≤l 1≤3,R包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Sn、Hf、Ta、W和Pb中的至少一种,M包括F、Cl、Br中的至少一种。
- 根据权利要求1或3所述的正极活性材料,其中,所述磷酸基钠盐材料包括NaFePO 4、Na 3V 2(PO 4) 3、Na 2FeP 2O 7、Na 2MnP 2O 7、NaCoP 2O 7、Na 7V 3(P 2O 7) 4、Na 2FePO 4F、Na 3V 2(PO 4) 2F 3、Na 4Fe 3(PO 4) 2(P 2O 7)、Na 4Mn 3(PO 4) 2(P 2O 7)、Na 4Co 3(PO 4) 2(P 2O 7)、Na 4Ni 3(PO 4) 2(P 2O 7)、Na 7V 4(PO 4)(P 2O 7) 4中的至少一种。
- 根据权利要求1或2所述的正极活性材料,其具有如下特征中的至少一种:(5)所述壳层材料的厚度为50nm~400nm;(6)所述壳层材料在所述正极活性材料中的质量含量为1%至10%;(7)所述核层材料在所述正极活性材料中的质量含量为90%至99%。
- 根据权利要求1或2所述的正极活性材料,其具有如下特征中的至少一种:(8)所述碳材料包括碳纳米管、石墨烯、碳纤维、天然石墨、人造石墨中的至少一种;(9)所述碳材料包括含氧基团,所述含氧基团选自羧基、羟基和醚基中的至少一种;(10)所述碳材料包括含氧基团,所述碳材料中的氧原子的质量含量≥0.1%;(11)所述导电基体材料为碳材料。
- 根据权利要求6所述的正极活性材料,其中,所述导电基体材料在所述正极活性材料中的质量含量为1%至10%。
- 权利要求1所述的正极活性材料,其中,所述正极活性材料具有如下特征中的至少一种:(12)所述正极活性材料在20MPa压力下的电阻率为0.005Ω·cm至100Ω·cm;(13)所述正极活性材料的平均粒径为5μm至20μm;(14)所述正极活性材料的克容量为100mAh/g至180mAh/g。
- 一种电化学装置,包括正极极片、负极极片、隔离膜及电解液,其中,所述正极极片包括权利要求1~8任一项所述的正极活性材料。
- 一种电子设备,包括权利要求9所述的电化学装置。
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