CN112952080A - Application of tripolyphosphoric acid mixed transition metal sodium salt in preparation of lithium ion battery or zinc ion battery - Google Patents
Application of tripolyphosphoric acid mixed transition metal sodium salt in preparation of lithium ion battery or zinc ion battery Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an application of tripolyphosphoric acid mixed transition metal sodium salt in preparation of a lithium ion battery or a zinc ion battery. The chemical formula of the trimeric phosphoric acid mixed transition metal sodium salt is as follows: na (Na)xB3‑ xCyD2‑yP3O11Wherein B is K, Li, Ca, Rb or Cs; x is more than 0 and less than or equal to 3; C. d is Mn, Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Al, Mg, Ru, Rh. Tc, In and Mo, y is In the range of 0-2. The invention relates to a method for synthesizing a high-performance multifunctional secondary battery electrode material, which is suitable for industrial production, by utilizing a sol-gel method. The tripolyphosphoric acid mixed transition metal sodium salt can be used for anodes or cathodes of various rocking chair type batteries (zinc ion, sodium ion or lithium ion batteries), has multiple functions, high performance, high working voltage and the like, is beneficial to simplifying a production line and reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of electrode materials of ion batteries, and particularly relates to a tripolyphosphoric acid mixed transition metal sodium salt (Na)xB3-xCyD2-yP3O11) The application in the preparation of lithium ion batteries or zinc ion batteries.
Background
Lithium ion batteries have excellent electrochemical properties, and thus have become one of the most mature energy storage devices developed at present and are widely applied to various small portable electronic devices, and meanwhile, have gradually begun to be applied to the field of power energy sources such as hybrid vehicles and electric vehicles. With the increasing use of lithium ion batteries, the price of lithium resources and the inherent resource limitations thereof are attracting people's attention. At the same time, sodium and lithium have many similar chemical properties, since they are adjacent to and in the same main group of the periodic table. In addition, the reserves of sodium and zinc elements on the earth are very abundant. The distribution is very wide. Therefore, sodium ion batteries and zinc ion batteries have rapidly attracted the attention of scientists due to their low cost characteristics, and are expected to become another popular energy storage system following lithium ion batteries.
Compared with lithium ion batteries, sodium ion batteries have several distinct advantages: 1) because the sodium element, the lithium element and related compounds thereof have similar physicochemical properties, the sodium ion battery and the lithium ion battery have similar working principles. Scientists can use the research experience of the past lithium ion battery for reference to quickly develop the sodium ion battery with excellent comprehensive performance, so that the product development cycle of the sodium ion battery is shorter than expected; 2) the content of sodium element in the crust is ranked sixth, in addition, the ocean is more inexhaustible sodium element, the resource is very rich, the preparation is simple, and compared with the lithium ion battery, the method has obvious cost advantage in the aspect of raw materials; 3) the electrode potential of the metal sodium is about 0.3V lower than that of the metal lithium, so that the electrolyte with lower decomposition potential can be utilized, and meanwhile, the aqueous electrolyte can be developed, flammable organic electrolyte is abandoned, and the safety of a battery cell is improved. However, sodium ion batteries also have significant disadvantages. Firstly, the radius of sodium ions is much larger than that of lithium ions, so that the sodium ions are not easy to freely deintercalate in an electrode material; secondly, the relative atomic mass of sodium ions is much larger than that of lithium ions, so that the specific capacity of the sodium ion battery under the same system is generally lower than that of the lithium ion battery; finally, while the lower electrode potential gives sodium-ion batteries a variety in electrolyte selection, it also results in sodium-ion batteries generally having lower energy densities than lithium-ion batteries. Although the sodium ion battery has the defects, the sodium ion battery has great development potential and application prospect in a power grid-level (MWh) energy storage power station system with low requirement on volume energy density due to the advantages of concealable yoghurts, abundant resources and low cost.
In general, zinc ion batteries are mainly aqueous batteries. Since the radius of the zinc ions is slightly smaller than that of the sodium ions, theoretically, the sodium ions can be freely extracted from the material, the zinc ions can also be freely extracted from the material, and the diaphragm does not need to be replaced. The zinc ion battery has the advantages that: water can be used as a solvent of the electrolyte, and compared with organic liquid used by sodium ion batteries and lithium ion batteries, the electrolyte is easier to obtain and has low cost. Meanwhile, organic liquid pollutes the environment and is very flammable, and water is safer to use as a solvent.
The application of polyanionic material is an effective scheme for solving the stability problem of the positive electrode material of the sodium-ion battery, taking polyanionic phosphate material as an example, the tetrahedral structure formed by combining stronger P-O bonds tightly restrains oxygen ions around phosphorus ions, so that the material has better thermal stability. However, the material has poor electron and ion conductivities, and is not suitable for large current charging and discharging, and although the electron conductivity is greatly improved by doping, carbon coating and the like, the ion conductivity is still low.
The tripolyphosphoric acid mixed transition metal sodium salt can be used as a positive electrode material of a sodium ion battery, but no document reports the application of the material in other ion battery electrode materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a tripolyphosphoric acid mixed transition metal sodium salt (Na)xB3-xCyD2-yP3O11) The application in the preparation of lithium ion batteries or zinc ion batteries.
The invention relates to a method for synthesizing a high-performance multifunctional secondary battery electrode material, which is suitable for industrial production, by utilizing a sol-gel method. Meanwhile, the tripolyphosphoric acid mixed transition metal sodium salt can be used for anodes or cathodes of various rocking chair type batteries, and is beneficial to simplifying production lines and reducing production cost.
The purpose of the invention is realized by the following technical scheme:
the application of the tripolyphosphoric acid mixed transition metal sodium salt in the preparation of the lithium ion battery or the zinc ion battery is characterized in that the chemical formula of the tripolyphosphoric acid mixed transition metal sodium salt is as follows: na (Na)xB3-xCyD2-yP3O11Wherein B is K, Li, Ca, Rb or Cs; x is in the range 0 < x.ltoreq.3 (preferably 0.01. ltoreq. x.ltoreq.3); C. d is Mn, Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Al, Mg, Ru, Rh, Tc, In, Mo, y is In the range of 0-2. The crystal structure of the material belongs to an orthorhombic system, and the space group is P2 12121. When x is 3, C is Mn, and y is 2, the chemical formula is Na3Mn2P3O11The unit cell parameters are:
further, the chemical formula of the tripolyphosphoric acid mixed transition metal sodium salt is Na3Mn2P3O11、Na2.8K0.2Mn2P3O11、Na3Mn1.6Ni0.4P3O11、Na3Mn1.6Fe0.4P3O11Or Na3Mn1.8Ni0.2P3O11。
When the lithium ion battery is prepared, the tripolyphosphoric acid mixed transition metal sodium salt is used for preparing a lithium ion battery cathode material;
when the zinc ion battery is prepared, the tripolyphosphoric acid mixed transition metal sodium salt is used for preparing the positive electrode material of the zinc ion battery.
The preparation method of the tripolyphosphoric acid mixed transition metal sodium salt comprises the following steps:
1) mixing precursors: mixing organic chelating agent, sodium source compound, B source compound, C source compound, D source compound, and phosphoric acid source compound with NaxB3-xCyD2-yP3O11In the chemical formula, Na, B, C, D and P are mixed uniformly according to the stoichiometric ratio, a proper amount of deionized water is added to form sol, and the sol is stirred under the heating of water bath until liquid is evaporated and wet gel is formed;
2) pretreatment: drying the wet gel obtained in the step 1) in an air atmosphere below 150 ℃ to obtain dry gel, grinding to obtain powder, treating for 3-6 h at 200-400 ℃ in air, reducing atmosphere or inert atmosphere, naturally cooling and grinding to obtain a powdery material;
3) sintering reaction: grinding the powdery material treated in the step 2) uniformly again, treating the powdery material for 8-12 h at 500-700 ℃ in air, reducing atmosphere or inert atmosphere, and naturally cooling to obtain a tripolyphosphoric acid mixed transition metal sodium salt or a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt; wherein, in the presence of air, the tripolyphosphoric acid mixed transition metal sodium salt is obtained; and in an inert atmosphere or a reducing atmosphere, obtaining the carbon-coated tripolyphosphate mixed transition metal sodium salt.
Preferably, the organic chelating agent in step 1) comprises citric acid (C)6H8O7) Ascorbic acid (C)6H8O6) Oxalic acid (H)2C2O4) Ethylene Diamine Tetraacetic Acid (EDTA) and ethylene diamine tetraacetic acid disodium (EDTA-2Na), wherein the added substance accounts for 100-300% of the sum of the metal ion substances (mole number) in the added C source compound and D source compound; further 200% of the sum of the amounts (moles) of the metal ion species in the C source compound and the D source compound added.
Preferably, the sodium source compound described in step 1) includes, but is not limited to, chlorides, oxides, hydroxides, and the like of sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate, sodium phosphate, sodium pyrophosphate, sodium oxalate, and sodium;
preferably, the B source compound described in step 1) includes, but is not limited to, chlorides, oxides, hydroxides, etc. of carbonate B salt, acetate B salt, sulfate B salt, nitrate B salt, phosphate B salt, pyrophosphate B salt, oxalate B salt, and B;
preferably, the C source compound described in step 1) includes, but is not limited to, carbonate C salt, acetate C salt, sulfate C salt, nitrate C salt, phosphate C salt, pyrophosphate C salt, oxalate C salt, and C chloride, oxide, hydroxide, etc.;
preferably, the D source compound described in step 1) includes, but is not limited to, chlorides, oxides, hydroxides, etc. of carbonate D salt, acetate D salt, sulfate D salt, nitrate D salt, phosphate D salt, pyrophosphate D salt, oxalate D salt and D;
preferably, the phosphate source compound described in step 1) includes, but is not limited to, ammonium dihydrogen phosphate (NH)4H2PO4) Diammonium hydrogen phosphate ((NH)4)2HPO4) Ammonium phosphate ((NH)4)3PO4) And phosphorus pentoxide (P)2O5) At least one of (1).
Preferably, the temperature of the water bath heating in the step 1) is 60-100 ℃; further 80 ℃;
preferably, the drying temperature in the air atmosphere in the step 2) is 70-150 ℃; further 150 ℃;
preferably, in the step 2), the treatment is carried out for 4-8 h at 300-500 ℃ in air, reducing atmosphere or inert atmosphere; further, processing for 5h at 350 ℃ in air, reducing atmosphere or inert atmosphere;
preferably, in the step 3), the treatment is carried out for 8-12 h at 500-800 ℃ in air, reducing atmosphere or inert atmosphere; further processing for 8h at 600 ℃ in air, reducing atmosphere or inert atmosphere.
Preferably, the reducing atmosphere in step 2) and 3) includes, but is not limited to, hydrogen (H)2) Ammonia (NH)3) Carbon monoxide (CO), Ar/H2Mixed gas or He/H2One of the mixed gases; further, 5% hydrogen/argon mixture gas was used.
Preferably, the inert atmosphere in step 2) or 3) comprises nitrogen (N)2) Argon (Ar), carbon dioxide (CO)2) Or helium (He).
Compared with the prior art, the invention has the following advantages and effects:
(1) the tripolyphosphoric acid mixed transition metal sodium salt synthesized by the method can be used for the positive electrode or the negative electrode of a zinc ion battery, a sodium ion battery and a lithium ion battery, has multiple functions, and can reduce the matched production cost.
(2) The invention has high performance and high working voltage. Taking x as 3, y as 1.6, C as Mn, D as Fe, and taking it as the positive electrode material of the sodium ion battery as an example, charging and discharging with 0.1C rate (12mA/g), the discharging voltage plateau is 3.5V, and when the working voltage windows are 2.0-4.3V, 1.5-4.3V, and 1.5-4.5V, the first discharging capacity respectively reaches 97, 107, and 140 mAh/g.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product of example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the product of example 1 of the present invention.
FIG. 3 is a thermogravimetric analysis of the material prepared in example 1 of the present invention.
FIG. 4 is a schematic view of a charge-discharge curve of a positive electrode material of a sodium ion battery assembled by the material prepared in example 1, wherein the charge-discharge multiplying power is 12mA/g, and the charge-discharge voltage is 1.8-4.3V.
FIG. 5 is a schematic view of a charge/discharge curve of a zinc ion battery anode material assembled with the material prepared in example 1 of the present invention, wherein the charge/discharge current density is 12mA/g, the charge/discharge voltage of the first turn is 0.3-1.8V, and then is changed to 0.3-1.75V.
FIG. 6 is a schematic diagram of the rate charging and discharging curve and the cycling performance after the capacity of the positive electrode material of the zinc ion battery assembled by the material prepared in example 1 of the present invention is stable.
FIG. 7 is a charge/discharge curve diagram of the negative electrode material of the lithium ion battery assembled by the material prepared in example 1, wherein the charge/discharge current density is 100mA/g, and the charge/discharge voltage is 0.01-3V.
FIG. 8 is an X-ray diffraction pattern of the product of example 2 of the present invention
FIG. 9 is a schematic view of a charge/discharge curve of a zinc ion battery anode material assembled with the material prepared in example 2 of the present invention, wherein the charge/discharge current density is 12mA/g, the charge/discharge voltage of the first turn is 0.3-1.8V, and then is changed to 0.3-1.75V.
FIG. 10 is a charge/discharge curve diagram of the negative electrode material of the lithium ion battery assembled with the material prepared in example 2, wherein the charge/discharge current density is 100mA/g, and the charge/discharge voltage is 0.01-3V.
FIG. 11 is an X-ray diffraction pattern of the product of example 3 of the present invention.
FIG. 12 is a scanning electron micrograph and an elemental distribution spectrum of a product of example 3 of the present invention. .
FIG. 13 is a charge/discharge curve diagram of the positive electrode material of the sodium ion battery assembled by the material prepared in example 3 of the present invention, wherein the charge/discharge current density is 12mA/g, and the charge/discharge voltage is 1.5-4.3V.
FIG. 14 is a first charging and discharging curve diagram of the positive electrode material of the sodium ion battery assembled by the material prepared in example 3 of the present invention, wherein the charging and discharging current density is 12mA/g, and the charging and discharging voltage is 2.0-4.3V, 1.5-4.3V, and 1.5-4.5V.
FIG. 15 is a graph showing the charge/discharge curves of the positive electrode material of a zinc ion battery assembled with the material prepared in example 3, wherein the charge/discharge current density is 12mA/g, the charge/discharge voltage for the first turn is 0.3-1.8V, and the voltage is changed to 0.3-1.75V.
FIG. 16 is a charge/discharge curve diagram of the negative electrode material of the lithium ion battery assembled with the material prepared in example 3, wherein the charge/discharge current density is 100mA/g, and the charge/discharge voltage is 0.01-3V.
FIG. 17 is an X-ray diffraction pattern of the product of example 4 of the present invention.
FIG. 18 is a graph showing the charge/discharge curves of the positive electrode material of a zinc ion battery assembled with the material prepared in example 4 of the present invention, wherein the charge/discharge current density is 12mA/g, the charge/discharge voltage for the first turn is 0.3-1.8V, and the voltage is changed to 0.3-1.75V.
FIG. 19 is a charge/discharge curve diagram of the negative electrode material of the lithium ion battery assembled with the material prepared in example 4 of the present invention, wherein the charge/discharge current density is 100mA/g, and the charge/discharge voltage is 0.01-3V.
Fig. 20 is a schematic diagram of the rate charge-discharge curve and the cycle performance after the capacity of the lithium ion battery anode material assembled by the material prepared in example 4 of the present invention is stable.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
Will CH3COONa、Mn(CH3COO)2And NH4H2PO4According to the proportion of Na: mn: p is 3: 2: 3, adding citric acid monohydrate with the amount being twice of the amount of the Mn element as a chelating agent, adding deionized water for dissolving, and performing magnetic stirring and drying at the constant temperature of 80 ℃ to obtain wet gel;
then drying the mixture in an oven at 150 ℃ for 12h to obtain dry gel; grinding to obtain powder;
presintering the product in 5% hydrogen-argon mixed gas at 350 ℃ for 5h, naturally cooling, grinding, and uniformly grinding to obtain a powdery material; grinding again, and then burning for 8h at 600 ℃ in a 5% hydrogen-argon mixed atmosphere to obtain carbon-coated trimeric phosphoric acid mixed transition metal sodium salt (manganese) (Na)3Mn2P3O11)。
The XRD pattern of the product obtained in this example was collected on a Bruker D8 ADVANCE powder crystal diffractometer with Cu-K α (λ ═ 0.154nm) as the light source. The scanning speed is 3 degrees per minute, and the scanning angle is 10 degrees to 80 degrees 2 theta. The XRD pattern of the product obtained in the embodiment is shown in figure 1, and the figure shows that the pure-phase orthorhombic tripolyphosphoric acid mixed transition metal sodium salt (manganese) material is synthesized by using a sol-gel method, no impurity peak exists in the spectrogram, and the product purity is high. The scanning electron micrograph of this product is shown in FIG. 2.
The material is tested to be black powder at normal temperature. Experiments show that the material is insoluble in water and ethanol and is not easy to absorb water and deliquesce.
The thermogravimetric and differential thermal analysis (TG-DTA) test curve of the product of this example was collected on a microcomputer thermal balance of the HTG-1 model of the Beijing Hengjiu scientific Instrument factory (HENVEN), with a temperature rise rate of 10 ℃/min. FIG. 3 shows the thermal analysis (TG-DTA) curve of the material of this example in the air atmosphere at a temperature range of 100 ℃ to 900 ℃. It can be seen from the figure that the material has a weight loss platform with a weight loss of 16% when heated to about 350 ℃, and the material can be considered that the carbon material coated on the surface is oxidized in the air to form carbon dioxide, and it can also be shown that the product in this embodiment is actually a carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese) electrode material.
In the case of a sodium ion battery, the electrochemical performance test process of the material in this example was performed by assembling a button cell and performing a constant current charge and discharge method. The button cell mould is CR 2032. Mixing a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese) material, acetylene black and polyvinylidene fluoride according to a mass ratio of 7: 2: 1, uniformly mixing in N-methyl pyrrolidone solution, coating on aluminum foil, fully drying, and cutting into a battery pole piece as a positive electrode. The cathode is taken as a metal sodium sheet, and the electrolyte is 1mol/L NaClO4In which 5% by weight of FEC (fluoroethylene carbonate) was added as an additive to a solution of ethylene carbonate/diethyl carbonate (EC/DME, 1:1 by volume). And packaging the battery pole piece and other materials into a button sodium ion battery in a glove box filled with high-purity argon, finally taking out the battery, and performing constant-current charge-discharge test by using a high-precision charge-discharge instrument, wherein the current density is 12mA/g, and the test voltage range is 1.8-4.3V. The carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese)The charge-discharge curve of the material used as the positive electrode of the sodium-ion battery is shown in figure 4, and as can be seen from figure 4, when the charge voltage is 1.8-4.3V, the specific discharge capacity can reach 90mAh/g, and the material has very good capacity characteristics.
In the case of a zinc ion battery, the electrochemical performance test process of the material in this example was performed by assembling a half cell and performing a constant current charge and discharge method. Mixing a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese) material, acetylene black and polyvinylidene fluoride according to a mass ratio of 7: 2: 1, uniformly mixing in N-methyl pyrrolidone solution, coating on titanium foil, fully drying, and cutting into a battery pole piece as a positive electrode. The battery mould is a button cell CR2032, the cathode is a metal zinc sheet, and the electrolyte is 3mol/L ZnSO4A deionized water solution of (a). Packaging the battery pole piece and other materials in the air to form the button zinc ion battery, performing constant current charge and discharge test by using a high-precision charge and discharge instrument, wherein the current density is 12mA/g, the charge and discharge voltage of the first circle is 0.3-1.8V, then changing to 0.3-1.75V, and performing residual test in the voltage interval. The charging and discharging curve of the carbon-coated mixed transition metal sodium tripolyphosphate (manganese) electrode material as the positive electrode of the zinc ion battery is shown in figure 5, and the figure shows that the carbon-coated mixed transition metal sodium tripolyphosphate (manganese) electrode material can have specific capacity of 100mAh/g after being activated. The multiplying power performance curve of the constant current charge and discharge test with the current density of 10mA/g, 20mA/g, 50mA/g, 100mA/g, 200mA/g and 500mA/g and finally returning to 10mAh/g is shown in figure 6, and as can be seen from the figure, after the large current circulates and returns to the small current, the initial capacity can be returned, and the multiplying power circulation performance is better.
In the case of a lithium ion battery, the carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese) material, the acetylene black, and the polyvinylidene fluoride in the present embodiment are mixed in a mass ratio of 7: 2: 1, uniformly mixing in an N-methyl pyrrolidone solution, coating on a copper foil, fully drying, and cutting into a battery pole piece serving as a negative electrode; the positive electrode is a metal lithium sheet. And packaging the battery pole piece into a button type lithium ion battery in a glove box filled with high-purity argon, finally taking out the battery, and performing constant current charge-discharge test by using a high-precision charge-discharge instrument. The current density is 100mA/g, and the test interval is 0.01-3V. The charge-discharge curve of the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese) material as the negative electrode of the lithium ion battery is shown in figure 7. The charge and discharge test results show that the charge and discharge curve of the negative electrode material is shown in figure 7 within the voltage range of 0.01-3V. As can be seen from the figure, the carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese) material has higher reversible specific capacity (400 mAh/g).
Example 2
Will CH3COONa、CH3COOK、Mn(CH3COO)2And NH4H2PO4According to the proportion of Na: k: mn: p ═ 2.8: 0.2: 2: 3, adding citric acid monohydrate with the amount being twice of that of the Mn element as a chelating agent, adding deionized water for dissolving, and performing magnetic stirring and drying at the constant temperature of 80 ℃ to obtain wet gel;
then drying the mixture in an oven at 150 ℃ for 12h to obtain dry gel; grinding to obtain powder;
presintering the product in 5% hydrogen-argon mixed gas at 350 ℃ for 5h, naturally cooling, grinding, and uniformly grinding to obtain a powdery material; grinding again, and igniting for 8h at 600 deg.C under 5% hydrogen-argon atmosphere to obtain carbon-coated sodium (potassium manganese) (Na) tripolyphosphate mixed transition metal2.8K0.2Mn2P3O11)。
The XRD pattern of the product obtained in this example was collected on a Bruker D8 ADVANCE powder crystal diffractometer with Cu-K α (λ ═ 0.154nm) as the light source. The scanning speed is 3 degrees per minute, and the scanning angle is 10 degrees to 80 degrees 2 theta. The XRD pattern of the product obtained in the embodiment is shown in figure 8, and the figure shows that the pure-phase orthorhombic mixed transition metal sodium tripolyphosphate (potassium manganese) material is synthesized by a sol-gel method, no impurity peak exists in the spectrogram, and the product purity is high.
In the case of a zinc ion battery, the electrochemical performance test process of the material in this example was performed by assembling a half cell and performing a constant current charge and discharge method. Mixing the carbon-coated tripolyphosphate with transition goldBelongs to sodium salt (potassium manganese) materials, acetylene black and polyvinylidene fluoride according to the mass ratio of 7: 2: 1, uniformly mixing in N-methyl pyrrolidone solution, coating on titanium foil, fully drying, and cutting into a battery pole piece as a positive electrode. The battery mould is a button cell CR2032, the negative electrode is a metal zinc sheet, and the electrolyte is 3mol/LZnSO4A deionized water solution of (a). Packaging the battery pole piece and other materials in the air to form the button zinc ion battery, performing constant current charge and discharge test by using a high-precision charge and discharge instrument, wherein the current density is 12mA/g, the charge and discharge voltage of the first circle is 0.3-1.8V, then changing to 0.3-1.75V, and performing residual test in the voltage interval. The charge-discharge curve of the tripolyphosphoric acid mixed transition metal sodium salt (potassium manganese) electrode material as the anode of the zinc ion battery is shown in figure 9, and the figure shows that the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (potassium manganese) material can have the specific capacity of 70mAh/g after being activated.
In the case of a lithium ion battery, the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (potassium manganese) material, acetylene black, and polyvinylidene fluoride in the present example were mixed in a mass ratio of 7: 2: 1, uniformly mixing in an N-methyl pyrrolidone solution, coating on a copper foil, fully drying, and cutting into a battery pole piece serving as a negative electrode; the positive electrode is a metal lithium sheet. And packaging the battery pole piece into a button type lithium ion battery in a glove box filled with high-purity argon, finally taking out the battery, and performing constant current charge-discharge test by using a high-precision charge-discharge instrument. The current density is 100mA/g, and the test interval is 0.01-3V. The charge-discharge curve of the carbon-coated tripolyphosphate mixed transition metal sodium salt (potassium manganese) material when used as the negative electrode of the lithium ion battery is shown in figure 10. The charge and discharge test results show that the charge and discharge curve of the negative electrode material is shown in figure 10 within the voltage range of 0.01-3V. As can be seen from the figure, the carbon-coated tripolyphosphate mixed transition metal sodium salt (potassium manganese) material has higher reversible specific capacity (300 mAh/g).
Example 3
Will CH3COONa、FeSO4、Mn(CH3COO)2And NH4H2PO4According to the proportion of Na: fe: mn: p is 3: 0.4: 1.6: 3, and adding Mn and Fe elementsUsing citric acid monohydrate twice the sum of the molar number of the elements as a chelating agent, adding deionized water for dissolving, and magnetically stirring and drying at the constant temperature of 80 ℃ to obtain wet gel;
then drying the mixture in an oven at 150 ℃ for 12h to obtain dry gel; grinding to obtain powder;
presintering the product in 5% hydrogen-argon mixed gas at 350 ℃ for 5h, naturally cooling, grinding, and uniformly grinding to obtain a powdery material; grinding again, and burning at 600 deg.C for 8 hr in 5% hydrogen-argon mixed atmosphere to obtain carbon-coated sodium manganese iron tripolyphosphate mixed transition metal (Na)3Mn1.6Fe0.4P3O11)。
The XRD pattern of the product obtained in this example was collected on a Bruker D8 ADVANCE powder crystal diffractometer with Cu-K α (λ ═ 0.154nm) as the light source. The scanning speed is 3 degrees per minute, and the scanning angle is 10 degrees to 80 degrees 2 theta. The XRD pattern of the product obtained in this example is shown in fig. 11, which shows that pure phase, orthorhombic sodium tripolyphosphate mixed transition metal (ferromanganese) material is synthesized by the sol-gel method, and the spectrum has no impurity peak and high product purity. The scanning electron micrograph and the element distribution map of the product are shown in figure 12, and it can be seen that the carbon element is uniformly distributed on the product, and the product is a carbon-coated tripolyphosphate mixed transition metal sodium salt (ferromanganese) material.
In the case of a sodium ion battery, the electrochemical performance test process of the material in this example was performed by assembling a button cell and performing a constant current charge and discharge method. Mixing a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (ferromanganese) material, acetylene black and polyvinylidene fluoride according to a mass ratio of 7: 2: 1, uniformly mixing in N-methyl pyrrolidone solution, coating on aluminum foil, fully drying, and cutting into a battery pole piece as a positive electrode. The cell mould is a button cell mould CR2032, the negative electrode is a metal sodium sheet, and the electrolyte is 1mol/L NaClO4With 5% by weight of FEC (fluoroethylene carbonate) as additive. Packaging the battery pole piece and other materials in a glove box filled with high-purity argon to form a button sodium ion battery, finally taking out the battery, and utilizing high-precision charging and dischargingThe instrument performs constant current charge and discharge tests. The test voltage range is 1.5-4.3V, and the current density is 12 mA/g. The charge-discharge curve of the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (ferromanganese) material is shown in figure 13, and as can be seen from figure 13, when the charge voltage is 1.5-4.3V, the specific discharge capacity can reach 107mAh/g, and the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (ferromanganese) material has very good capacity characteristics. Meanwhile, as can be seen from FIG. 14, the first discharge capacities of the batteries were 97 mAh/g and 140mAh/g, respectively, when the charging voltages were 2.0V to 4.3V and 1.5V to 4.5V.
In the case of a zinc ion battery, the electrochemical performance test process of the material in this example was performed by assembling a half cell and performing a constant current charge and discharge method. Mixing a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (ferromanganese) material, acetylene black and polyvinylidene fluoride according to a mass ratio of 7: 2: 1, uniformly mixing in N-methyl pyrrolidone solution, coating on titanium foil, fully drying, and cutting into a battery pole piece as a positive electrode. The battery mould is a button cell CR2032, the negative electrode is a metal zinc sheet, and the electrolyte is 3mol/LZnSO4In deionized water solution. Packaging the battery pole piece and other materials in the air to form the button zinc ion battery, performing constant current charge and discharge test by using a high-precision charge and discharge instrument, wherein the current density is 12mA/g, the charge and discharge voltage of the first circle is 0.3-1.8V, then changing to 0.3-1.75V, and performing residual test in the voltage interval. The charge-discharge curve of the carbon-coated mixed transition metal sodium tripolyphosphate (ferromanganese) electrode material as the positive electrode of the zinc ion battery is shown in fig. 15, and it can be seen from the graph that the carbon-coated mixed transition metal sodium tripolyphosphate (ferromanganese) electrode material can have a specific capacity of 105mAh/g after being activated.
In the case of a lithium ion battery, the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (ferromanganese) material, the acetylene black, and the sodium alginate in the embodiment are mixed in a mass ratio of 7: 2: 1, uniformly mixing the materials in deionized water, coating the mixture on copper foil, fully drying the copper foil, and cutting the copper foil into a battery pole piece serving as a negative electrode; the positive electrode is a metal lithium sheet. And packaging the battery pole piece into a button type lithium ion battery in a glove box filled with high-purity argon, finally taking out the battery, and performing constant current charge-discharge test by using a high-precision charge-discharge instrument. The current density is 100mA/g, and the test interval is 0.01-3V. The charge-discharge curve of the carbon-coated tripolyphosphate mixed transition metal sodium salt (ferromanganese) material as the negative electrode of the lithium ion battery is shown in figure 16. The charge and discharge test results show that the charge and discharge curve of the negative electrode material is shown in figure 16 within the voltage range of 0.01-3V. As can be seen from the figure, the carbon-coated tripolyphosphate mixed transition metal sodium salt (ferromanganese) material has higher reversible specific capacity (560 mAh/g).
Example 4
Will CH3COONa、Ni(CH3COO)2、Mn(CH3COO)2And NH4H2PO4According to the proportion of Na: ni: mn: p is 3: 0.4: 1.6: 3, adding citric acid monohydrate which is twice the sum of the mole numbers of Mn and Ni elements and is used as a chelating agent, adding deionized water for dissolving, and performing magnetic stirring and drying at the constant temperature of 80 ℃ to obtain wet gel;
then drying the mixture in an oven at 150 ℃ for 12h to obtain dry gel; grinding to obtain powder;
presintering the product in 5% hydrogen-argon mixed gas at 350 ℃ for 5h, naturally cooling, grinding, and uniformly grinding to obtain a powdery material; grinding again, and then burning for 8h at 600 ℃ in a 5% hydrogen-argon mixed atmosphere to obtain carbon-coated trimeric phosphoric acid mixed transition metal sodium salt (manganese-nickel) (Na)3Mn1.6Ni0.4P3O11)。
The XRD pattern of the product obtained in this example was collected on a Bruker D8 ADVANCE powder crystal diffractometer with Cu-K α (λ ═ 0.154nm) as the light source. The scanning speed is 3 degrees per minute, and the scanning angle is 10 degrees to 80 degrees 2 theta. The XRD pattern of the product obtained in the embodiment is shown in figure 17, and the figure shows that the pure-phase orthorhombic tripolyphosphoric acid mixed transition metal sodium salt (manganese nickel) material is synthesized by using a sol-gel method, no impurity peak exists in the spectrogram, and the product purity is high.
In the case of a zinc ion battery, the electrochemical performance test process of the material in this example was performed by assembling a half cell and performing a constant current charge and discharge method. Mixing a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese nickel) material, acetylene black and polyvinylidene fluoride according to a mass ratio of 7: 2: 1 in N-methyl pyrrolidone solutionAnd after the combination, coating the titanium foil on the titanium foil, fully drying the titanium foil, and cutting the titanium foil into a battery pole piece serving as a positive electrode. The battery mould is a button cell CR2032, the cathode is a metal zinc sheet, and the electrolyte is 3mol/L ZnSO4Dissolved in deionized water. Packaging the battery pole piece and other materials in the air to form the button zinc ion battery, performing constant current charge and discharge test by using a high-precision charge and discharge instrument, wherein the current density is 12mA/g, the charge and discharge voltage of the first circle is 0.3-1.8V, then changing to 0.3-1.75V, and performing residual test in the voltage interval. The charge-discharge curve of the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese nickel) electrode material as the positive electrode of the zinc ion battery is shown in figure 18, and the figure shows that the carbon-coated manganese sodium diphosphate material can have the specific capacity of 80mAh/g after being activated.
In the case of a lithium ion battery, the carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese nickel) material, the acetylene black, and the sodium alginate in the embodiment are mixed in a mass ratio of 70: 15: 15, uniformly mixing the mixture in deionized water, coating the mixture on copper foil, fully drying the copper foil, and cutting the copper foil into a battery pole piece serving as a negative electrode; the positive electrode is a metal lithium sheet. And packaging the battery pole piece into a button type lithium ion battery in a glove box filled with high-purity argon, finally taking out the battery, and performing constant current charge-discharge test by using a high-precision charge-discharge instrument. The current density is 100mA/g, and the test interval is 0.01-3V. The charge-discharge curve of the carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese nickel) material as the negative electrode of the lithium ion battery is shown in figure 19. The charge and discharge test results show that the charge and discharge curve of the negative electrode material is shown in FIG. 19 within the voltage range of 0.01-3V. As can be seen from the figure, the carbon-coated tripolyphosphate mixed transition metal sodium salt (manganese nickel) material has higher reversible specific capacity (170 mAh/g)). The multiplying power performance curve of the carbon-coated tripolyphosphoric acid mixed transition metal sodium salt (manganese nickel) electrode material as a lithium ion battery cathode for sequentially carrying out constant current charge and discharge tests with current densities of 10mA/g, 20mA/g, 50mA/g, 100mA/g and 200mA/g and finally returning to 10mAh/g is shown in figure 20.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The application of the tripolyphosphoric acid mixed transition metal sodium salt in the preparation of the lithium ion battery or the zinc ion battery is characterized in that: the chemical formula of the tripolyphosphoric acid mixed transition metal sodium salt is as follows: na (Na)xB3-xCyD2-yP3O11Wherein B is K, Li, Ca, Rb or Cs; x is more than 0 and less than or equal to 3; C. d is Mn, Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Al, Mg, Ru, Rh, Tc, In, Mo, y is In the range of 0-2.
2. Use according to claim 1, characterized in that: the chemical formula of the trimeric phosphoric acid mixed transition metal sodium salt is Na3Mn2P3O11、Na2.8K0.2Mn2P3O11、Na3Mn1.6Ni0.4P3O11、Na3Mn1.6Fe0.4P3O11Or Na3Mn1.8Ni0.2P3O11。
3. Use according to claim 1 or 2, characterized in that:
when the lithium ion battery is prepared, the tripolyphosphoric acid mixed transition metal sodium salt is used for preparing a lithium ion battery cathode material;
when the zinc ion battery is prepared, the tripolyphosphoric acid mixed transition metal sodium salt is used for preparing the positive electrode material of the zinc ion battery.
4. Use according to claim 1 or 2, characterized in that:
the preparation method of the tripolyphosphoric acid mixed transition metal sodium salt comprises the following steps:
1) mixing precursors: mixing organic chelating agent, sodium source compound, B source compound, C source compound, D source compound, and phosphoric acid source compound with NaxB3-xCyD2-yP3O11In the chemical formula, Na, B, C, D and P are mixed uniformly according to the stoichiometric ratio, a proper amount of deionized water is added to form sol, and the sol is stirred under the heating of water bath until liquid is evaporated and wet gel is formed;
2) pretreatment: drying the wet gel obtained in the step 1) in an air atmosphere below 150 ℃ to obtain dry gel, grinding to obtain powder, treating for 3-6 h at 200-400 ℃ in air, reducing atmosphere or inert atmosphere, naturally cooling and grinding to obtain a powdery material;
3) sintering reaction: grinding the powdery material treated in the step 2) uniformly again, treating the powdery material for 8-12 h at 500-700 ℃ in air, reducing atmosphere or inert atmosphere, and naturally cooling to obtain a tripolyphosphoric acid mixed transition metal sodium salt or a carbon-coated tripolyphosphoric acid mixed transition metal sodium salt; wherein, in the presence of air, the tripolyphosphoric acid mixed transition metal sodium salt is obtained; and in an inert atmosphere or a reducing atmosphere, obtaining the carbon-coated tripolyphosphate mixed transition metal sodium salt.
5. Use according to claim 4, characterized in that:
the organic chelating agent in the step 1) comprises citric acid, ascorbic acid, oxalic acid, ethylene diamine tetraacetic acid and ethylene diamine tetraacetic acid, and the amount of the added substances is 100-300% of the sum of the amounts of the metal ions in the added C source compound and D source compound.
6. Use according to claim 5, characterized in that:
the amount of the added substance was 200% of the sum of the amounts of the substances of the metal ions in the added C source compound and D source compound.
7. Use according to claim 4, characterized in that:
the sodium source compound in the step 1) includes, but is not limited to, carbonate sodium salt, acetate sodium salt, sulfate sodium salt, nitrate sodium salt, phosphate sodium salt, pyrophosphate sodium salt, oxalate sodium salt and chloride, oxide and hydroxide of sodium;
the B source compound in the step 1) comprises but is not limited to carbonate B salt, acetate B salt, sulfate B salt, nitrate B salt, phosphate B salt, pyrophosphate B salt, oxalate B salt and chloride, oxide and hydroxide of B;
the C source compound in the step 1) includes but is not limited to carbonate C salt, acetate C salt, sulfate C salt, nitrate C salt, phosphate C salt, pyrophosphate C salt, oxalate C salt and C chloride, oxide and hydroxide;
the D source compound in the step 1) comprises, but is not limited to carbonate D salt, acetate D salt, sulfate D salt, nitrate D salt, phosphate D salt, pyrophosphate D salt, oxalate D salt and chloride, oxide and hydroxide of D;
the phosphoric acid source compound in the step 1) includes, but is not limited to, at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and phosphorus pentoxide.
8. Use according to claim 4, characterized in that:
the water bath heating temperature in the step 1) is 60-100 ℃;
the drying temperature in the air atmosphere in the step 2) is 70-150 ℃;
in the step 2), treating for 4-8 h at 300-500 ℃ in air, reducing atmosphere or inert atmosphere;
in the step 3), the treatment is carried out for 8-12 h at 500-800 ℃ in air, reducing atmosphere or inert atmosphere.
9. Use according to claim 8, characterized in that:
the temperature of the water bath heating in the step 1) is 80 ℃;
the drying temperature in the air atmosphere in the step 2) is 150 ℃;
in the step 2), treating for 5 hours at 350 ℃ in air, reducing atmosphere or inert atmosphere;
in step 3), the treatment is carried out for 8h at 600 ℃ in air, a reducing atmosphere or an inert atmosphere.
10. Use according to claim 4, characterized in that:
reducing atmosphere described in step 2) and 3), including but not limited to hydrogen, ammonia, carbon monoxide, Ar/H2Mixed gas or He/H2One of the mixed gases;
the inert atmosphere in the step 2) and the step 3) comprises one of nitrogen, argon, carbon dioxide or helium.
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Application publication date: 20210611 |