CN109920979B - Positive plate and electrochemical cell - Google Patents
Positive plate and electrochemical cell Download PDFInfo
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- CN109920979B CN109920979B CN201711318082.4A CN201711318082A CN109920979B CN 109920979 B CN109920979 B CN 109920979B CN 201711318082 A CN201711318082 A CN 201711318082A CN 109920979 B CN109920979 B CN 109920979B
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Abstract
The application provides a positive plate and an electrochemical cell. The positive plate comprises a positive current collector and a positive membrane, the positive membrane is arranged on the positive current collector and comprises a positive active material, the positive active material comprises a Prussian blue material-conductive additive compound, and the molecular formula of the Prussian blue material is AxMy[M′(CN)6]zWherein A is one or more of alkali metal cations and alkaline earth metal cations, M is transition metal, M' is transition metal, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, and the resistivity of the positive electrode membrane is less than or equal to 400 omega cm. The resistivity of the anode membrane is controlled within a certain range, so that the conductivity of the anode membrane can be effectively improved, the capacity exertion of Prussian blue materials is facilitated, and the electrochemical cell has good rate performance, high initial capacity and good cycle performance.
Description
Technical Field
The application relates to the field of batteries, in particular to a positive plate and an electrochemical battery.
Background
Lithium ion batteries are widely used due to their advantages of high energy density, long cycle life, etc., but they still face many problems, among which the cost problem becomes one of the important reasons restricting their development. Sodium ion batteries have received great attention in recent years from research and industry as a new generation of electrochemical energy storage system that is a potential alternative to existing energy storage devices. How to improve the comprehensive performance of the sodium-ion battery and enable the sodium-ion battery to realize commercial production is an important research and development direction at present.
Disclosure of Invention
In view of the problems of the background art, an object of the present invention is to provide a positive electrode sheet and an electrochemical cell that achieve both good rate performance, high initial capacity, and good cycle performance.
In order to achieve the above object, in one aspect of the present application, the present application provides a positive plate, which includes a positive current collector and a positive membrane, the positive membrane is disposed on the positive current collector, the positive membrane includes a positive active material, the positive active material includes a prussian blue material-conductive additive compound, the prussian blue material has a molecular formula of axMy[M′(CN)6]zWherein A is one or more of alkali metal cations and alkaline earth metal cations, M is transition metal, M' is transition metal, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, and the resistivity of the positive electrode membrane is less than or equal to 400 omega cm.
In another aspect of the present application, the present application provides an electrochemical cell comprising a positive electrode sheet of one aspect of the present application.
Compared with the prior art, the beneficial effects of this application do:
the electrochemical cell selects the Prussian blue material-conductive additive compound as the positive active material, and simultaneously controls the resistivity of the positive membrane within a certain range, so that the rate performance of the electrochemical cell can be effectively improved, and the electrochemical cell has both higher initial capacity and good cycle performance.
Detailed Description
The positive electrode sheet and the electrochemical cell according to the present application will be described in detail below.
The positive electrode sheet according to the first aspect of the present application is first explained.
According to this application first aspect's positive plate includes anodal mass flow body and anodal diaphragm, anodal diaphragm set up in anodal mass flow body is last, anodal diaphragm includes anodal active material, anodal active material includes prussian blue class material-conductive additive complex, prussian blue class material's molecular formula is AxMy[M′(CN)6]zWherein, A is one or more of alkali metal cation and alkaline earth metal cation, M is transition metal, M' is transition metal, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, and z is more than 0 and less than or equal to 1. The resistivity of the positive electrode membrane is less than or equal to 400 omega cm, preferably the resistivity of the positive electrode membrane is 15 omega cm-400 omega cm, and more preferably the resistivity of the positive electrode membrane is 30 omega cm-200 omega cm.
In the positive plate according to the first aspect of the present application, the resistivity of the positive plate is controlled within a certain range, which can significantly improve the overall performance of the electrochemical cell, and thus the electrochemical cell has good rate performance, high initial capacity and good cycle performance. If the resistivity of the positive electrode membrane is too high, the diffusion and transmission rates of electrons and ions in the positive electrode membrane in a series of processes of charging and discharging, from the inside of positive electrode active material particles to the surface of the positive electrode active material particles, from the surface of one positive electrode active material particle to the surface of another positive electrode active material particle, from the positive electrode active material particles to an electrolyte interface, from the positive electrode active material particles to a positive electrode current collector interface and the like are slow, so that the dynamic performance, the rate capability and the initial capacity of the electrochemical cell are poor. Meanwhile, due to poor electronic and ionic conductivity of the prussian blue material, the capacity exertion of the prussian blue material is seriously influenced by too high resistivity, and further the initial capacity, the cycle performance and the rate performance of the electrochemical cell are also seriously influenced.
In the positive electrode sheet according to the first aspect of the present application, the kind of the conductive additive is not particularly limited, and may be selected according to actual needs. Specifically, the conductive additive may be one or more selected from inorganic conductive agents and conductive polymers. Preferably, the conductive additive is a mixture of an inorganic conductive agent and a conductive polymer.
In the positive electrode sheet according to the first aspect of the present application, if the content of the inorganic conductive agent is too large, due to its strong liquid absorption property, a uniformly dispersed mobile phase is generally not formed in the in-situ synthesis of the prussian blue-based material-conductive additive composite, resulting in poor feasibility and practicality of preparing the composite; if the content of the inorganic conductive agent is too small, the purpose of improving the initial capacity, the cycle performance and the rate performance of the electrochemical cell cannot be achieved. Preferably, the content of the inorganic conductive agent is 0.1-5% of the total mass of the prussian blue material-conductive additive compound, and further preferably, the content of the inorganic conductive agent is 0.5-3% of the total mass of the prussian blue material-conductive additive compound.
In the positive electrode sheet according to the first aspect of the present application, if the content of the conductive polymer is too high, the crystal structure and the chemical composition of the prepared prussian blue material may have defects, which may affect the capacity performance of the prussian blue material, and meanwhile, the presence of the defects in the crystal structure of the prussian blue material may also cause a decrease in crystallinity, that is, an order degree of arrangement of electrons and atoms may decrease, which may hinder diffusion and movement of electrons in the prussian blue material, and may further affect the resistivity of the positive electrode sheet; if the content of the conductive polymer is too small, the purpose of improving the initial capacity, the cycle performance and the rate performance of the electrochemical cell cannot be achieved. Preferably, the content of the conductive polymer is 0.1-15% of the total mass of the prussian blue material-conductive additive compound, and further preferably, the content of the conductive polymer is 1-3% of the total mass of the prussian blue material-conductive additive compound.
In the positive electrode sheet according to the first aspect of the present application, preferably, the inorganic conductive agent may be one or more selected from acetylene black, conductive carbon black, ketjen black, carbon nanotubes, carbon fibers, carbon nanowires, graphene, carbon nanoribbons, and conductive graphite.
In the positive electrode sheet according to the first aspect of the present application, preferably, the conductive polymer may be selected from one or more of polypyrrole, polyaniline, polythiophene, polyphenylene sulfide, and derivatives thereof. Among them, the polythiophene derivative is preferably polyethylenedioxythiophene-polystyrene sulfonate (PEDOT/PSS).
In the positive electrode sheet according to the first aspect of the present application, the positive electrode sheet further includes a conventional conductive agent and a binder, and the conventional conductive agent and the binder are uniformly dispersed in the positive electrode sheet. Specifically, the conventional conductive agent, the prussian blue material-conductive additive compound and the binder are uniformly dispersed in a solvent to prepare positive electrode slurry, and the positive electrode slurry is dried to remove the solvent to form the positive electrode membrane. The kind of the conventional conductive agent is not particularly limited and may be selected according to actual requirements. Specifically, the conventional conductive agent can be selected from one or more of acetylene black, Super-P, carbon nanotubes, Ketjen black and conductive graphite, and the content of the conventional conductive agent is preferably greater than or equal to 5% of the total mass of the positive electrode membrane, so as to further provide a good conductive channel in the positive electrode membrane, control the resistivity of the positive electrode membrane and improve the performance of the electrochemical cell. Further preferably, the content of the conventional conductive agent is 5-20% of the total mass of the positive electrode diaphragm. The kind of the binder is not particularly limited, and may be selected according to actual requirements. Specifically, the binder can be selected from one or more of water-soluble binders and oil-soluble binders.
In the positive electrode sheet according to the first aspect of the present application, the particle diameter D50 of the prussian blue material is preferably 0.5 to 5 μm. The prussian blue material has a larger particle size, so that the transmission path of electrons and ions in the prussian blue material particles is prolonged, the electron conductivity and the ion conductivity of the anode membrane are reduced, and the resistivity of the anode membrane is also higher; the prussian blue material has small particle size, and although the prussian blue material has good electron conductivity and ion conductivity, the prussian blue material has low crystallinity generally, defects of a crystal structure and a chemical composition are increased, and the prussian blue material with small particle size has high specific surface area, so that the prussian blue material has poor dispersibility and serious liquid absorption phenomenon in positive electrode slurry, and simultaneously, the prussian blue material with small particle size has heavy granular sensation, uneven surface density and reduced compaction density, so that the cycle life and the safety performance of the electrochemical battery are influenced to a certain extent.
In the positive electrode sheet according to the first aspect of the present disclosure, the prussian blue material is a highly crystalline cubic phase structure or hexagonal phase structure, and the prussian blue material having an amorphous structure or a low crystallinity hinders diffusion and transmission of electrons and ions due to disordered accumulation of ions, so that the positive electrode sheet has poor electron conductivity and ion conductivity, a high resistivity, and poor comprehensive performance of an electrochemical cell.
In the positive electrode sheet according to the first aspect of the present application, the thickness of the positive electrode membrane sheet is 10 μm to 200 μm, and preferably, the thickness of the positive electrode membrane sheet is 60 μm to 120 μm. The thickness of the positive membrane is small, and the energy density of the electrochemical cell is low; the thickness of the positive membrane is large, the positive membrane is easy to crack, so that the resistivity of the positive membrane is increased, the electrochemical performance of the electrochemical battery is affected, and the positive membrane can fall off from a positive current collector under severe conditions, so that the electrochemical battery cannot be normally used.
In the positive electrode sheet according to the first aspect of the present application, the prussian blue-based material-conductive additive composite may be obtained by in-situ synthesis. In the prussian blue material-conductive additive compound, at least one part of conductive additive is coated on the surface of the prussian blue material.
Preferably, if the conductive additive is an inorganic conductive agent, the preparation method of the prussian blue material-conductive additive composite may be: dissolving a precursor metal M salt in a solvent to prepare a solution I; dissolving hexacyanometallate formed by metal M' and metal A and an inorganic conductive agent in a solvent to obtain a solution II; and mixing the solution I and the solution II, reacting for a period of time to obtain a precipitate, separating and collecting the precipitate, washing and drying to obtain the prussian blue material-conductive additive compound.
Preferably, if the conductive additive is a conductive polymer, the preparation method of the prussian blue material-conductive additive composite may be: dissolving a precursor metal M salt in a solvent to prepare a solution I; dissolving hexacyanometallate formed by metal M' and metal A, a monomer for synthesizing a conductive polymer and an initiator in a solvent to obtain a solution II; and mixing the solution I and the solution II, reacting for a period of time to obtain a precipitate, separating and collecting the precipitate, washing and drying to obtain the prussian blue material-conductive additive compound.
Preferably, if the conductive additive is a conductive polymer, the preparation method of the prussian blue material-conductive additive composite can also be: dissolving a precursor metal M salt in a solvent to prepare a solution I; uniformly dispersing hexacyanometallate formed by metal M' and metal A and conductive polymer colloid in a solvent to obtain a solution II; and mixing the solution I and the solution II, reacting for a period of time to obtain a precipitate, separating and collecting the precipitate, washing and drying to obtain the prussian blue material-conductive additive compound.
Next, an electrochemical cell according to the second aspect of the present application will be described.
An electrochemical cell according to a second aspect of the present application includes the positive electrode sheet according to the first aspect of the present application, the negative electrode sheet, an electrolyte, and a separator and the like.
In the electrochemical cell according to the second aspect of the present application, the electrochemical cell may be a lithium ion cell, a sodium ion cell, a potassium ion cell, a zinc ion cell, or an aluminum ion cell. In the embodiments of the present application, only the embodiment in which the electrochemical cell is a sodium ion cell is shown, but the present application is not limited thereto.
In the sodium ion battery, the negative electrode sheet may include a negative electrode current collector and a negative electrode membrane disposed on the negative electrode current collector and containing a negative electrode active material. The negative active material can be one or more selected from carbon materials, alloy materials, transition metal oxides and sulfides, phosphorus-based materials and titanate materials. In particular, the carbon material may be selected from hard carbon, soft carbon,one or more of amorphous carbon and nanostructured carbon materials; the alloy material can be selected from one or more of Si, Ge, Sn, Pb and Sb; the transition metal oxides and sulfides have the general formula MxNyWherein M is one or more of Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb and V, and N is O or S; the phosphorus-based material can be one or more of red phosphorus, white phosphorus and black phosphorus; the titanate material may be selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3One or more of them.
In the sodium ion battery, the negative electrode sheet further comprises a conductive agent and a binder, and the types of the conductive agent and the binder are not particularly limited and can be selected according to actual requirements.
In a sodium ion battery, the electrolyte may be a liquid electrolyte, which may include a sodium salt, an organic solvent, and optionally an electrolyte additive. The type of the sodium salt is not particularly limited, and can be selected according to actual requirements. Specifically, the sodium salt may be selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) Sodium hexafluoroborate (NaBF)6) One or more of sodium trifluoromethanesulfonate and sodium trifluoromethanesulfonate (NaTFSI). The kind of the organic solvent is not particularly limited, and may be selected according to actual requirements. Specifically, the organic solvent may be one or more selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The kind of the electrolyte additive is not particularly limited, and the electrolyte additive can be selectively added according to actual requirements.
In the sodium ion battery, the material of the isolation membrane is not limited and can be selected according to actual requirements. Specifically, the separator may be selected from one of polypropylene film, polyethylene/polypropylene/polyethylene composite film, nonwoven fabric film, and glass fiber film.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Example 1
(1) Preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; PEDOT/PSS was uniformly dispersed in deionized water and sodium ferrocyanide (Na) was added4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6PEDOT/PSS, among others, Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive PEDOT/PSS is 0.1% of the total mass of the compound.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
(2) Preparation of negative plate
Dissolving a negative electrode active material hard carbon, a conductive agent acetylene black and a binder Styrene Butadiene Rubber (SBR) in deionized water according to a mass ratio of 90:5:5, and fully stirring and uniformly mixing to obtain a negative electrode slurry; and then coating the negative electrode slurry on a copper foil of a negative current collector, and then drying, cold pressing and stripping to obtain the negative plate.
(3) Preparation of the electrolyte
The method comprises the steps of dissolving ethylene carbonate with the same volume in propylene carbonate, and then dissolving a proper amount of sodium salt sodium perchlorate in a mixed solvent to obtain the electrolyte.
(4) Preparation of the separator
Polyethylene film was selected as the barrier film.
(5) Preparation of sodium ion battery
And winding the positive plate, the negative plate and the isolating film to prepare a battery core, then filling the battery core into a battery packaging shell, then injecting electrolyte, and preparing the sodium ion battery by processes of formation, standing and the like.
Example 2
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
The content of PEDOT/PSS is 1% of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Example 3
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
The content of PEDOT/PSS is 3% of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Example 4
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
The content of PEDOT/PSS is 10% of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Example 5
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
The content of PEDOT/PSS is 15% of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Example 6
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing polypyrrole in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Polypyrrole, Prussian blue material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of polypyrrole as a conductive additive is 1% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 7
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes in which the Prussian blue type material Na2MnFe(CN)6Having a particle diameter D50 of 1 μm, and a conductive additive of carbon nanotubesThe amount was 1% of the total mass of the compound.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 8
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing polypyrrole and carbon nano tube in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Polypyrrole/carbon nanotubes, in which the prussian blue material Na2MnFe(CN)6The particle diameter D50 of the composite is 1 μm, the content of the conductive additive polypyrrole is 0.5 percent of the total mass of the composite, and the content of the conductive additive carbon nano tube is 0.5 percent of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 9
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) is dissolved in deionized waterForming a first solution in the sub-water; the polyaniline is uniformly dispersed in deionized water, and sodium ferrocyanide (Na) is added4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Polyaniline, wherein Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive polyaniline is 3% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 10
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; dispersing Ketjen black in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Ketjen black, wherein Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of conductive additive Keqin black is 1% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 11
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes in which the Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive carbon nanotube is 3% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 12
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes, among which prussian blue-based materialsNa2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive carbon nano tube is 5% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 13
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6The particle diameter D50 was 0.4. mu.m.
Example 14
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6The particle diameter D50 was 0.5. mu.m.
Example 15
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6The particle diameter D50 of (1) was 2 μm.
Example 16
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6The particle diameter D50 of (1) was 5 μm.
Example 17
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6The particle diameter D50 of (1) was 6 μm.
Example 18
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The mass ratio of the prussian blue material-conductive additive compound, the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 85:5: 10.
Example 19
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The mass ratio of the prussian blue material-conductive additive compound, the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 70:20: 10.
Example 20
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Dissolving the prussian blue material-conductive additive compound prepared in the embodiment 2, a conventional conductive agent carbon nano tube and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain positive electrode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 21
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Dissolving the prussian blue material-conductive additive compound prepared in the embodiment 2 and a conventional conductive agent Keqin black and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain positive electrode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Example 22
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Dissolving the prussian blue material-conductive additive compound prepared in the embodiment 2, acetylene black serving as a conventional conductive agent and polyvinylidene fluoride serving as a binder in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain positive electrode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 1
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
The content of PEDOT/PSS is 20% of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Comparative example 2
The content of PEDOT/PSS is 0.05 percent of the total mass of the Prussian blue material-conductive additive compound, and the mass ratio of the Prussian blue material-conductive additive compound to the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 80:10: 10.
Comparative example 3
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes in which the Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive carbon nano tube is 0.05% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound, a conventional conductive agent Super P and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 4
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; sodium ferrocyanide (Na)4Fe(CN)6·10H2O) is uniformly dispersed in deionized water to form a solution II; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, and washing and drying the precipitate to obtain the Prussian blue material Na2MnFe(CN)6Wherein, Prussian blue material Na2MnFe(CN)6The particle diameter D50 of (1) was 1 μm.
Dissolving the Prussian blue material prepared in the above step, a conventional conductive agent, namely Super P, and a binder, namely polyvinylidene fluoride, in a solvent, namely N-methyl pyrrolidone, according to a mass ratio of 80:10:10, and fully stirring and uniformly mixing to obtain positive electrode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 5
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; sodium ferrocyanide (Na)4Fe(CN)6·10H2O) is uniformly dispersed in deionized water to form a solution II; make the solution slowlySlowly dropwise adding the solution II into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the Prussian blue material Na2MnFe(CN)6Wherein, Prussian blue material Na2MnFe(CN)6The particle diameter D50 of (1) was 1 μm.
Dissolving the Prussian blue material prepared in the above step, a conventional conductive agent, namely Super P, and a binder, namely polyvinylidene fluoride, in a solvent, namely N-methyl pyrrolidone, according to a mass ratio of 70:20:10, and fully stirring and uniformly mixing to obtain positive electrode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 6
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes in which the Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive carbon nano tube is 5% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 90:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 7
The sodium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
Mixing manganese chloride (MnCl)2·4H2O) dissolving in deionized water to form a first solution; uniformly dispersing carbon nanotubes in deionized water, and adding sodium ferrocyanide (Na)4Fe(CN)6·10H2O) to form a second solution; slowly dripping the solution I into the solution II for reaction, collecting the obtained precipitate after the reaction is finished, washing and drying to obtain the prussian blue material-conductive additive compound Na2MnFe(CN)6Carbon nanotubes in which the Prussian blue type material Na2MnFe(CN)6The particle diameter D50 is 1 μm, and the content of the conductive additive carbon nano tube is 25% of the total mass of the composite.
Dissolving the prepared prussian blue material-conductive additive compound and a binder polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to a mass ratio of 90:10, and fully stirring and uniformly mixing to obtain anode slurry; and then uniformly coating the positive slurry on a positive current collector aluminum foil, and then drying, cold-pressing and splitting to obtain the positive plate.
Comparative example 8
The sodium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The mass ratio of the prussian blue material-conductive additive compound, the conventional conductive agent Super P and the adhesive polyvinylidene fluoride in the positive electrode slurry is 87:3: 10.
The following describes the testing process of the sodium ion battery.
(1) Resistivity testing of positive membranes
The positive electrode sheets of examples 1 to 22 and comparative examples 1 to 8 were cut into a square having a size of 10cm × 10cm, and a sheet resistance tester (one-point method, test area 153.94 mm)2) Measuring the resistance of the positive electrode diaphragm, taking 4 positive electrode diaphragm samples for each group, taking an average value after testing the resistance value of 10 points of each sample, taking the average value as the resistance value R of the group of positive electrode diaphragms, and then calculating the resistivity of the positive electrode diaphragm according to rho ═ RS/L, wherein S is the area of the positive electrode diaphragm, and L is the thickness of the positive electrode diaphragm.
(2) Cycle performance testing of sodium ion batteries
At 25 ℃, the sodium ion batteries of examples 1 to 22 and comparative examples 1 to 8 were subjected to constant current charging at a rate of 0.5C until the voltage was 4.0V, then were subjected to constant voltage charging at a constant voltage of 4.0V until the current was 0.2C, then were allowed to stand for 5min, were subjected to constant current discharging at a rate of 0.5C until the voltage was 1.9V, and were allowed to stand for 5min, which was a cyclic charge and discharge process, and the discharge capacity of this time was recorded as the discharge capacity of the sodium ion battery at the 1 st cycle, i.e., the initial capacity of the sodium ion battery. And (3) carrying out 60-cycle charge and discharge tests on the sodium-ion battery according to the method, and detecting to obtain the discharge capacity of the 60 th cycle.
The capacity retention (%) of the sodium-ion battery after 60 cycles at 25 ℃ was equal to the discharge capacity at 60 cycles/discharge capacity at 1 cycle × 100%.
(3) Rate capability test of sodium ion battery
And at room temperature, charging the sodium ion battery to 4.0V at a constant current of a rate of 2C, then discharging the sodium ion battery to 1.9V at a constant current of a rate of the same size, and testing to obtain the 2C rate discharge capacity of the sodium ion battery. Each group tested 4 sodium ion cells each and the average was taken.
TABLE 1 parameters and results of Performance tests for examples 1-22 and comparative examples 1-8
From the data analysis in table 1, it can be seen that the resistivity of the positive membrane has a significant effect on the rate capability, initial capacity and cycle performance of the sodium ion battery. Comparative example 4 only uses prussian blue materials as positive active materials, and although a large amount of conventional conductive agents are added during slurry preparation, the resistivity of the positive membrane is still large, which is not beneficial to the capacity exertion of the prussian blue materials, and the cycle performance of the sodium ion battery is also poor. Comparative example 5 further increases the content of the conventional conductive agent on the basis of comparative example 4, and although the resistivity of the positive electrode membrane is reduced, because the electron conducting and ion conducting properties of the prussian blue material are poor, the increase of the content of the conventional conductive agent in the positive electrode slurry cannot fundamentally improve the diffusion and transmission of electrons and ions in the positive electrode membrane, and further cannot effectively improve the electrochemical properties of the sodium ion battery. Comparative examples 6 and 7 only coat a large amount of conductive additives on the surface of prussian blue materials, and conventional conductive agents are not added when the positive electrode slurry is prepared, so that the rate performance and the cycle performance of the sodium ion battery are poor, and the reason is limited by the preparation process on the one hand, even if a large amount of conductive additives are used when the composite is prepared, because of the strong liquid absorption property of the conductive additives, a uniformly dispersed mobile phase cannot be formed in a solvent, and the conductive additives cannot be uniformly coated on the surface of prussian blue material particles or cannot achieve the effect of uniform mixing in the process of in-situ synthesis of the composite, so that the conductivity and the ion conductivity of the prussian blue materials cannot be effectively improved; on the other hand, because a binder substance without conductivity is added when the positive electrode slurry is prepared, the interface resistance of the positive electrode membrane and the positive electrode current collector is increased when the positive electrode sheet is prepared, and these factors are factors hindering the movement of electrons and ions, so that the diffusion and transmission of electrons and ions between prussian blue material particles and at the interface of the positive electrode membrane and the positive electrode current collector cannot be effectively improved only by coating the conductive additive on the surface of the prussian blue material, and the overall effect of the sodium-ion battery is still poor.
In examples 1 to 22, when the prussian blue material-conductive additive composite is used as the positive electrode active material, in the charging and discharging processes, when electrons and ions diffuse from the inside of prussian blue material particles to the surface, and are transmitted from one particle surface to the adjacent particle surface, and in the opposite process, the conductive additive provides good channels for the diffusion and transmission of electrons and ions, so that the electron conductivity and ion conductivity of the positive electrode membrane can be remarkably improved, the resistivity of the positive electrode membrane is reduced, and the electrons and ions can be relatively and reversibly diffused and transmitted in the charging and discharging processes are ensured, so that the sodium ion battery has good rate capability, high initial capacity and good cycle performance.
In examples 1 to 22, it is understood that the performance improvement effect on the sodium ion battery is different depending on the kinds of the conductive additive and the conventional conductive agent. The effect of the conductive polymer on the improvement of the cycle performance of the sodium-ion battery is better than that of the inorganic conductive agent, probably because the long-chain structure of the conductive polymer can be connected with more Prussian blue material particles, so that the long-distance conductivity of the Prussian blue material can be effectively improved; on the other hand, the long-range network structure between the conductive polymer and the prussian blue material particles also plays a role in stabilizing the prussian blue material structure to a certain extent, inhibits the volume and structure changes possibly generated in the charge-discharge process, and is favorable for improving the cycle performance of the sodium-ion battery. The inorganic conductive agent has a better improvement effect on the rate capability of the sodium ion battery than that of the conductive polymer, and probably because the conductivity of the conductive polymer is slightly poor (the conductivity is close to that of a conventional semiconductor), and electrons and ions cannot be diffused and transmitted in time in the high-rate charge and discharge process of the sodium ion battery. Therefore, it is preferable that the conductive additive includes both the inorganic conductive agent and the conductive polymer, so that both long-range conductivity of the conductive polymer can be exerted and electrons and ions can be diffused and transported in time by virtue of excellent conductivity of the inorganic conductive agent.
Meanwhile, the influence of the dosage of the conductive additive on the resistivity of the positive electrode film is easy to understand. If the content of the conductive additive is small, the conductive additive cannot be uniformly coated on the surfaces of the prussian blue material particles, so that the electron conductivity and the ion conductivity of the positive electrode membrane cannot be effectively improved. The conductive additive, such as a conductive polymer, has a high content, and in the process of in-situ synthesizing the prussian blue material-conductive additive composite, the crystal growth of the prussian blue material is influenced due to the existence of excessive conductive polymers, so that the crystal structure and the chemical composition of the prussian blue material have defects, and the capacity exertion of the prussian blue material is influenced, and the initial capacity of the sodium-ion battery is reduced. In combination with the test results of comparative example 1, it can be seen that, although the resistivity of the positive electrode film is low, the crystal growth of the prussian blue material is affected due to the excessive amount of the conductive polymer coated on the surface of the prussian blue material, so that defects exist in the crystal structure and the chemical composition, and the capacity exertion of the prussian blue material is affected. However, the content of conductive additives such as inorganic conductive agents is high, and these inorganic conductive agents usually cannot form a uniformly dispersed mobile phase due to strong liquid absorption in the in-situ synthesis, which results in poor feasibility and practicability of preparing materials.
In examples 13 to 17, the particle size of prussian blue based material particles had some influence on the resistivity of the positive electrode sheet. The larger the particle size of the prussian blue-based material particle is, the longer the transport path of electrons and ions inside a single particle is, and thus the poorer the electron and ion conductivity of the positive electrode membrane is. However, in comparison, the influence of the particle size on the performance of the sodium-ion battery is smaller than the influence caused by the content of the conductive additive in the prussian blue material-conductive additive compound and the content of the conventional conductive agent in the positive electrode membrane.
In summary, the content of the conductive additive or the conventional conductive agent should be controlled within a certain range, so as to ensure that the electrochemical performance of the sodium ion battery can be improved, and on the other hand, the crystal and chemical structure of the prussian blue material are not damaged due to the use of too much conductive additive or conventional conductive agent, so that the normal diffusion and transmission channels of electrons and ions are not affected, the content of active sodium ions is reduced, the loading capacity of the prussian blue material in the positive electrode membrane is not reduced, the compaction density of the positive electrode membrane is not affected, and the energy density of the sodium ion battery is not lost. Therefore, in practical applications, the kinds and amounts of the conductive additive and the conventional conductive agent are selected as required.
Claims (15)
1. A positive electrode sheet, comprising:
a positive current collector; and
the positive electrode diaphragm is arranged on the positive electrode current collector;
it is characterized in that the preparation method is characterized in that,
the positive electrode membrane comprises a positive electrode active material;
the positive active material comprises a prussian blue material-conductive additive complex;
the molecular formula of the prussian blue material is AxMy[M′(CN)6]zWherein, A is one or more of alkali metal cation and alkaline earth metal cation, M is transition metal, M' is transition metal, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, and z is more than 0 and less than or equal to 1;
the resistivity of the positive electrode diaphragm is less than or equal to 400 omega cm;
the conductive additive is selected from a mixture of an inorganic conductive agent and a conductive polymer;
the content of the inorganic conductive agent is 0.1-5% of the total mass of the compound;
the content of the conductive polymer is 0.1-15% of the total mass of the compound.
2. The positive electrode sheet according to claim 1, wherein the positive electrode sheet has a resistivity of 15 Ω -cm to 400 Ω -cm.
3. The positive electrode sheet according to claim 1, wherein the positive electrode sheet has a resistivity of 30 Ω -cm to 200 Ω -cm.
4. The positive electrode sheet according to claim 1, wherein in the composite:
the content of the inorganic conductive agent is 0.1-5% of the total mass of the compound,
the content of the conductive polymer is 1-3% of the total mass of the compound.
5. The positive electrode sheet according to claim 1, wherein in the composite:
the content of the inorganic conductive agent is 0.5 to 3 percent of the total mass of the compound;
the content of the conductive polymer is 0.1-15% of the total mass of the compound.
6. The positive electrode sheet according to claim 1, wherein in the composite:
the content of the inorganic conductive agent is 0.5 to 3 percent of the total mass of the compound;
the content of the conductive polymer is 1-3% of the total mass of the compound.
7. The positive electrode sheet according to claim 1,
the inorganic conductive agent is selected from one or more of acetylene black, conductive carbon black, Ketjen black, carbon nano tubes, carbon fibers, carbon nano wires, graphene, carbon nano belts and conductive graphite;
the conductive polymer is selected from one or more of polypyrrole, polyaniline, polythiophene, polyphenylene sulfide and derivatives thereof.
8. The positive electrode sheet according to claim 1, wherein the positive electrode sheet further comprises a conventional conductive agent.
9. The positive electrode sheet according to claim 8, wherein the content of the conventional conductive agent is 5% or more of the total mass of the positive electrode sheet.
10. The positive electrode sheet according to claim 9, wherein the content of the conventional conductive agent is 5% to 20% of the total mass of the positive electrode sheet.
11. The positive electrode sheet according to claim 1, wherein the particle diameter D50 of the Prussian blue material is 0.5 to 5 μm.
12. The positive electrode sheet according to claim 1, wherein the prussian blue-based material has a cubic phase structure or a hexagonal phase structure.
13. The positive electrode sheet according to claim 1, wherein the thickness of the positive electrode film sheet is 10 μm to 200 μm.
14. The positive electrode sheet according to claim 1, wherein the thickness of the positive electrode film sheet is 60 μm to 120 μm.
15. An electrochemical cell comprising the positive electrode sheet according to any one of claims 1 to 14.
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