CN113937342A - Wide-temperature-range sodium ion battery based on iron-based polyanionic anode and tin-carbon cathode - Google Patents
Wide-temperature-range sodium ion battery based on iron-based polyanionic anode and tin-carbon cathode Download PDFInfo
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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
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a wide-temperature sodium ion battery based on an iron-based polyanionic anode and a tin-carbon cathode. In the wide-temperature sodium ion battery, the positive electrode material is one or a mixture of several iron-based polyanionic positive electrode materials; the negative electrode is a mixture of metallic tin and a carbon-based material; the electrolyte contains an ether solvent, takes an organic sodium salt and/or an inorganic sodium salt as a solute, and shows good ionic conductivity in a wider temperature range (-70-160 ℃). The wide-temperature sodium ion battery is low in cost, can stably work within the temperature range of-70-160 ℃, has high energy density, shows good cycle performance, power characteristics and rate capability, and can be used as an energy storage device in areas with high cold, high temperature and large environmental temperature change.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a sodium ion battery.
Background
In recent years, lithium ion batteries have been rapidly developed and widely used in various industries. However, the growing demand of people and the shortage of lithium resources directly restrict the development of lithium ion batteries, especially the development of large-scale energy storage, such as new energy vehicles and smart power grids, and provide new requirements for the development of secondary batteries. The sodium atom and the lithium atom have similar atomic structures and chemical properties, the reserves of the global sodium element are extremely rich, and the sodium-ion battery also has higher specific energy and low production cost. Therefore, as lithium ion batteries are limited in their wide application by the influence of lithium resources and production costs, sodium ion batteries having similar electrochemical properties have been the focus of attention of researchers. At present, the performance of some sodium ion battery electrode materials is improved remarkably, and the sodium ion battery electrode materials are likely to partially replace lithium ion batteries which are commercialized at present.
In a sodium ion battery system containing ether electrolyte, metal tin and most carbon-based materials show rapid reaction kinetics and stable cycle performance due to solvent co-intercalation, and the cost of the current commercial sodium ion battery can be effectively reduced by using the tin-carbon composite electrode material. The iron-based polyanionic anode material has adjustable voltage, lower cost, higher cycling stability and good rate performance, and is one of ideal choices of the anode material of the sodium-ion battery.
However, it is noteworthy that: the stable potential window of the diethylene glycol dimethyl ether solvent is limited, and the stable potential window is higher than 4V (vs. Na/Na)+) Decomposition occurs and thus it cannot be applied to a high voltage sodium ion battery. The invention combines the composite material with a tin-carbon mixed negative electrode and an iron-based polyanionic compound positive electrode material for the first time (the working voltage is less than 4V). According to the invention, the iron-based polyanionic compound is used as the anode, the tin-carbon composite material is used as the cathode, the ether solvent is used as the electrolyte, and the full battery is assembled, so that the sodium ion battery with low cost and stable circulation can be obtained. Meanwhile, due to the high boiling point and the low melting point of the ether solvent, the full battery can work within the temperature range of-70-160 ℃.
Disclosure of Invention
The invention aims to provide a sodium ion battery which has wide working temperature range, low cost, long cycle life, high energy density and excellent rate performance.
The sodium ion battery provided by the invention comprises a positive electrode, a negative electrode and electrolyte; wherein the anode material is one or a mixture of several iron-based polyanion compounds; the negative electrode is a mixture of metallic tin and a carbon-based material; the electrolyte contains an ether solvent, organic sodium salt and/or inorganic sodium salt are/is used as solute, and high ionic conductance is shown in a wide temperature range (-70-160 ℃); and has the characteristics of high boiling point and low freezing point; in the electrolyte, the concentration range of sodium ions is 0.01-10 mol/L.
Its working principle is mainly in the course of charging and discharging, Na+Embedding and releasing between the positive electrode and the negative electrode back and forth: during charging, Na+The electrolyte is separated from the positive electrode and is embedded into the negative electrode through the electrolyte, and the negative electrode is in a sodium-rich state; the opposite is true during discharge.
In the invention, the electrochemical performance of the positive active material can be improved by nanocrystallization (less than or equal to 1 micron) and surface carbon coating.
In the invention, the ether solvent is one or a mixture of several of diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, methyl nonafluoro n-butyl ether and octafluoropentyl-tetrafluoroethyl ether, and the mixed solvent mainly has the function of adjusting the viscosity of the electrolyte at high temperature or low temperature, the corresponding ionic conductivity and the oxidation resistance at high voltage.
In the invention, the solute comprises organic sodium salt and inorganic sodium salt, including but not limited to one or more of sodium hexafluorophosphate, sodium bis (trifluoromethylsulfonyl imide), sodium triflate, sodium tetrachloroborate, sodium perchlorate, sodium tetrafluoroborate, sodium nitrate, sodium hexafluoroantimonate, sodium benzoate, sodium p-toluenesulfonate, sodium bifluorosulfonimide, sodium tetrachloroaluminate, sodium tetrachloroferrite and sodium tetraphenylborate.
In the invention, the electrolyte also contains one or more of borate, sulfite, sultone, fluoroethylene ester and polyoxyethylene ether as a film forming additive. The additive mainly functions to facilitate the formation of a uniform SEI film, thereby reducing interfacial resistance.
In the invention, the electrolyte also contains one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, isopropylphenyl diphenyl phosphate, cresyl diphenyl phosphate, hexamethoxy phosphazene, tris (2, 2,2 ‒ trifluoroethyl) phosphate, bis (2, 2,2 ‒ trifluoroethyl) methyl phosphoric acid, and (2, 2, 2-trifluoroethyl) diethyl ester and hexamethyl phosphoramide as an electrolyte flame retardant additive.
In the invention, the positive electrode active material can be one or a mixture of several iron-based polyanion-type compounds, and the iron-based polyanion-type compounds are selected from Na4Fe3(PO4)2P2O7，Na2FePO4F，Na2FeP2O7，NaFePO4，Na2Fe(SO4)2And the like.
In the present invention, the Fe element in the positive electrode active material may be substituted by the Mn element.
In the invention, the negative active material is metallic tin or a mixture of metallic tin and a carbon-based material, and the carbon-based material is one or more selected from graphite, soft carbon, hard carbon, graphene, carbon nanotubes, carbon fibers and the like.
In the invention, the positive electrode and the negative electrode are respectively composed of an active substance, a conductive agent, a binder and a current collector.
In the invention, the current collector is one or a compound of more of a titanium mesh, a titanium foil, a stainless steel mesh, a porous stainless steel belt, a stainless steel foil, an aluminum mesh, carbon cloth, a carbon mesh, a carbon felt, a copper mesh and a copper foil.
In the invention, the binder is one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), water-soluble rubber, polyvinyl alcohol (PVA), polyacrylic acid (PAA), Sodium Alginate (SA) and acrylonitrile multipolymer (LA132/LA 133).
In the invention, the conductive additive is one or more of activated carbon, acetylene black, carbon nano tubes, carbon fibers, graphene, graphite and mesoporous carbon.
The wide-temperature sodium ion battery is low in cost, can stably work within the temperature range of-70-160 ℃, has high energy density, shows good cycle performance, power characteristics and rate capability, and can be used as an energy storage device in areas with high cold, high temperature and large environmental temperature change.
Detailed Description
To further clearly illustrate the technical solutions and advantages of the present invention, the present invention is described by the following specific examples, but the present invention is not limited to these examples.
Example 1
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FeP2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FeP2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6 mg cm-2. Next, metallic tin (Sn) is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (Sn): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 1 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 91 percent (shown in table 1) after 6000 cycles of circulation at the current density of 0.5C and the capacity retention rate reaches 90 percent (shown in table 2) after 10000 cycles of circulation at the current density of 10C at the normal temperature of 25 ℃. The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 90 mAh g at 25 ℃ at room temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 55 mAh g at the low temperature of-70 DEG C-1The capacity reaches 92 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 2
The electrolyte with wide temperature range is prepared by taking ethylene glycol dimethyl ether as a solvent, dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L, and adding 5 percent trimethyl phosphate as a flame retardant. With Na2FeP2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FeP2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 93 percent after 5000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 89 percent after 15000 cycles of circulation at the current density of 10C (see table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 89 mAh g at a temperature of 25 ℃-1(calculated based on the mass of the positive active material), the specific capacity is 56 mAh g at the low temperature of-70 DEG C-1The capacity reaches 93 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 3
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FeP2O7And mixing with active carbon as positive active material. The preparation of the positive electrode plate is as follows: according to Na2FeP2O7: conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6 mg cm-2. Next, metallic tin (Sn) and Hard Carbon (Hard Carbon) were used as negative electrode active materials. The preparation of the negative electrode slice is as follows: according to the active substance (Sn: hard carbon =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this embodiment, the negative electrodeThe coating weight of (2) was 1.5 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 89 percent after 8000 cycles of cycling at the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 88 percent after 12000 cycles of cycling at the current density of 10C (see table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 92 mAh g at 25 ℃ at room temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 59 mAh g at the low temperature of-70 DEG C-1The capacity reaches 94 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 4
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FePO4F as a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FePO4F) The method comprises the following steps Conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 5.5 mg cm-2. Next, a mixture of metallic tin (Sn) and hard carbon is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active substance (Sn: hard carbon =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 1.5 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reached 90% after 6000 cycles at 25 ℃ and 0.5C, and 91% after 15000 cycles at 10C (see Table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 107 mAh g at a room temperature of 25 deg.C-1(calculated based on the mass of the positive electrode active material), the specific capacity is 73 mAh g at the low temperature of-70 DEG C-1The capacity reaches 112 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 5
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FePO4F and active carbon mixture is used as the anode active material. The preparation of the positive electrode plate is as follows: according to Na2FePO4F: conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 89 percent (shown in a table 1) after 8000 cycles of circulation at the normal temperature of 25 ℃ and the current density of 0.5C, and the capacity retention rate reaches 86 percent (shown in a table 2) after 10000 cycles of circulation at the current density of 10C. The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 109 mAh g at 25 ℃ at room temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 71 mAh g at the low temperature of-70 DEG C-1The capacity reaches 115 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 6
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na4Fe3(PO4)2P2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)4Fe3(PO4)2P2O7): conductive agent (super P): binder (polyvinylidene fluoride PVDF) =80:10The slurry is mixed according to the proportion and coated on the surface of the aluminum foil to form the positive electrode plate. In this example, the coating amount of the positive electrode was 6.8 mg cm-2. Next, a mixture of metallic tin (Sn) and hard carbon is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active substance (Sn: hard carbon =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 1.5 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 92 percent (shown in table 1) after 4000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, and the capacity retention rate reaches 89 percent (shown in table 2) after 9000 cycles of circulation at the current density of 10C. The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 116 mAh g at 25 ℃ at normal temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity at the low temperature of-70 ℃ is 89 mAh g-1The capacity reaches 120 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 7
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na4Fe3(PO4)2P2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to Na4Fe3(PO4)2P2O7: conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6.8 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 86 percent after 9000 cycles of the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 92 percent after 10000 cycles of the current density of 10C (see table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 118 mAh g at 25 ℃ at normal temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 93 mAh g at the low temperature of-70 DEG C-1The capacity reaches 124 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 8
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FePO4F and Na4Fe3(PO4)2(P2O7) The mixture was used as a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FePO4F：Na4Fe3(PO4)2(P2O7) =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 5.5 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 91 percent (shown in a table 1) after 5000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, and the capacity retention rate reaches 88 percent (shown in a table 2) after 8000 cycles of circulation at the current density of 10C. The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 114 at 25 ℃ at room temperature mAh g-1(calculated based on the mass of the positive active material), the specific capacity is 96 mAh g at the low temperature of-70 DEG C-1The capacity reaches 120 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 9
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na2FePO4F and Na2FeP2O7The mixture was used as a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FePO4F：Na2FeP2O7=1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 5.5 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 90 percent after 6000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 87 percent after 15000 cycles of circulation at the current density of 10C (see table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 92 mAh g at 25 ℃ at room temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 81 mAh g at the low temperature of-70 DEG C-1The capacity reaches 97 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Example 10
The electrolyte with wide temperature range is obtained by taking ethylene glycol dimethyl ether as a solvent and dissolving sodium hexafluorophosphate in the ethylene glycol dimethyl ether according to the concentration of 1, 5 and 10 mol/L. With Na4Fe3(PO4)2(P2O7) With Na2FeP2O7The mixture was used as a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)4Fe3(PO4)2(P2O7)：Na2FeP2O7=1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF) =80:10: 10), and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6 mg cm-2. Next, a mixture of metallic tin (Sn) and graphite is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: as active material (Sn: graphite =1: 1): conductive agent (super P): and (3) mixing the slurry with a binder (sodium carboxymethylcellulose (CMC) =80:10: 10), and coating the slurry on the surface of copper foil to form the negative electrode plate. In this example, the coating amount of the negative electrode was 2 mg cm-2. And then, the glass fiber is taken as a battery diaphragm to assemble the sodium ion button battery. The capacity retention rate reaches 87 percent after 9000 cycles of the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 86 percent after 10000 cycles of the current density of 10C (see table 2). The charge and discharge test was carried out at a current density of 0.2C (calculated based on the mass of the negative electrode active material), and the specific capacity was 102 mAh g at 25 ℃ at normal temperature-1(calculated based on the mass of the positive electrode active material), the specific capacity is 84 mAh g at the low temperature of-70 DEG C-1The capacity reaches 107 mAh g at the high temperature of 160 DEG C-1(see Table 3).
Table 1 comparison of cycle performance of sodium ion batteries using different electrode materials and electrolytes
Table 2 comparison of cycle performance of sodium ion batteries using different electrode materials and electrolytes
Table 3 comparison of performance of sodium ion battery using different electrode materials and electrolyte at different temperatures
Claims (10)
1. A wide-temperature sodium ion battery based on an iron-based polyanionic anode and a tin-carbon cathode consists of an anode, a cathode and electrolyte; the anode material is one or a mixture of several iron-based polyanionic compounds; the negative electrode is a mixture of metallic tin and a carbon-based material; the electrolyte contains an ether solvent, organic sodium salt and/or inorganic sodium salt are/is used as solute, and high ionic conductance is shown within the temperature range of minus 70 ℃ to 160 ℃; in the electrolyte, the concentration of sodium ions is 0.01-10 mol/L.
2. The wide temperature sodium ion battery of claim 1, wherein the positive active material enhances its electrochemical performance by nanocrystallization and surface carbon coating.
3. The wide temperature range sodium ion battery of claim 1, wherein the ether solvent is selected from one or more of diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, methyl nonafluoro-n-butyl ether, and octafluoropentyl-tetrafluoroethyl ether.
4. The wide temperature sodium ion battery of claim 1, wherein the solute comprises organic and inorganic sodium salts selected from one or more of sodium hexafluorophosphate, sodium bis (trifluoromethylsulfonimide), sodium triflate, sodium tetrachloroborate, sodium perchlorate, sodium tetrafluoroborate, sodium nitrate, sodium hexafluoroantimonate, sodium benzoate, sodium p-toluenesulfonate, sodium difluorosulfonimide, sodium tetrachloroaluminate, sodium tetrachloroferrite, and sodium tetraphenylborate.
5. The wide temperature range sodium ion battery of claim 1, wherein the electrolyte further comprises one or more of borate esters, sulfite esters, sultone esters, fluoroethylene esters, and polyoxyethylether as a film forming additive.
6. The wide temperature sodium ion battery of claim 1, wherein the electrolyte further comprises one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, cumyl diphenyl phosphate, cresyl diphenyl phosphate, hexamethoxyphosphazene, tris (2, 2,2 ‒ trifluoroethyl) phosphate, bis (2, 2,2 ‒ trifluoroethyl) methyl phosphoric acid and (2, 2, 2. trifluoroethyl) diethyl ester, hexamethylphosphoramide as an electrolyte flame retardant additive.
7. The wide temperature sodium ion battery of claim 1, wherein the iron-based polyanionic compound is selected from Na4Fe3(PO4)2P2O7，Na2FePO4F，Na2FeP2O7，NaFePO4，Na2Fe(SO4)2。
8. The wide temperature sodium ion battery of claim 1, wherein the carbon-based material is selected from one or more of graphite, soft carbon, hard carbon, graphene, carbon nanotubes, and carbon fibers.
9. The wide temperature sodium ion battery of claim 1, wherein the positive and negative electrodes each comprise an active material, a conductive agent, a binder, and a current collector.
10. The wide temperature sodium ion battery of claim 1, wherein:
the current collector is one or a compound of more of a titanium mesh, a titanium foil, a stainless steel mesh, a porous stainless steel band, a stainless steel foil, an aluminum mesh, carbon cloth, a carbon mesh, a carbon felt, a copper mesh and a copper foil;
the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, water-soluble rubber, polyvinyl alcohol, polyacrylic acid, sodium alginate and acrylonitrile multipolymer;
the conductive additive is one or more of activated carbon, acetylene black, carbon nanotubes, carbon fibers, graphene, graphite and mesoporous carbon.
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