CN113745647A - Non-negative electrode rechargeable sodium ion secondary battery and manufacturing method thereof - Google Patents
Non-negative electrode rechargeable sodium ion secondary battery and manufacturing method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a negative-electrode-free rechargeable sodium ion secondary battery and a manufacturing method thereof, wherein the negative-electrode-free rechargeable sodium ion secondary battery comprises a shell, a diaphragm, a positive electrode plate and a negative electrode plate, wherein the diaphragm, the positive electrode plate and the negative electrode plate are wound inside the shell, and the diaphragm is positioned between the positive electrode plate and the negative electrode plate; the preparation method comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging; according to the invention, the material with the sodium fast ion conductor structure is used as the active substance to prepare the sodium ion battery, so that the sodium ion battery is beneficial to being applied to energy storage and power in a large scale, the application range of the sodium ion battery is improved, and meanwhile, in the preparation process, the finished battery material is placed at an inclined angle to be placed, so that the electrolyte is beneficial to being fully contacted with the pole piece, and the quality of the battery product is further improved.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a non-negative electrode rechargeable sodium ion secondary battery and a manufacturing method thereof.
Background
Lithium ion batteries have been widely used in various fields such as energy storage, electric vehicles, electric tools, mobile digital devices, and the like. With the widespread use of lithium ion batteries, especially the rapid development of the electric automobile market, lithium resources are largely consumed and are about to be exhausted. The current lithium ion battery technology has the problems of high price, poor material stability, poor long-cycle safety performance and the like in the large-scale energy storage stage. Meanwhile, considering the energy consumption of lithium ion battery material manufacturing, battery production and cycle, the lithium ion battery with 1kWh needs to consume about 400kWh of energy and generate about 75kg of carbon dioxide gas (equivalent to the amount of gas discharged by 35L of gasoline combustion), and the main energy consumption is the production of electrode materials. Therefore, the environmental benefits of lithium ion batteries can be gradually developed only after the batteries are cycled hundreds of times (> 400).
The crustal content of lithium element is only 0.0065%, and the global lithium storage of more than 76% is intensively distributed in south America. The lithium resource reserves are little, and the global distribution is uneven, so that the cost of the lithium ion battery is always high. The sodium element of the same main group has a content of about 2.8% in the shell, is 430 times as abundant as lithium resources, and has similar physicochemical properties with lithium. According to the principle of a lithium ion rocking chair type battery, a sodium ion-rich compound can be similar to a lithium ion-rich positive electrode material, can provide sodium ions which can be extracted and inserted and a structure, and is matched with corresponding electrolyte, a diaphragm and a negative electrode to form the room-temperature sodium ion battery. The development of sodium ion batteries provides an important direction for reducing the cost of secondary ion batteries. The sodium ion battery generates battery voltage through different potentials of positive and negative electrodes of the battery, realizes the embedding and emigration of sodium ions between the positive and negative electrodes, and completes charge storage and release.
The sodium ion battery is still in the initial starting stage, and compared with the lithium ion battery, the sodium ion battery has the advantages that: (1) the sodium salt raw material has abundant reserves and low price, and compared with the ternary cathode material of the lithium ion battery, the adopted ferro-manganese nickel-based cathode material has half of the raw material cost; (2) due to the characteristics of sodium salt, the low-concentration electrolyte (the electrolyte with the same concentration and the sodium salt conductivity higher than that of the lithium electrolyte by about 20%) is allowed to be used, so that the cost is reduced; (3) sodium ions do not form an alloy with aluminum, and the negative electrode can adopt aluminum foil as a current collector, so that the cost can be further reduced by about 8 percent, and the weight can be reduced by about 10 percent; (4) the sodium ion battery is allowed to discharge to zero volts due to its no over-discharge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, which is comparable with that of a lithium iron phosphate battery, but the cost advantage is obvious, and the sodium ion battery is expected to replace the traditional lead-acid battery in large-scale energy storage, so that the design of a negative-electrode-free rechargeable sodium ion secondary battery and a manufacturing method thereof are necessary.
Disclosure of Invention
The present invention is directed to a non-negative electrode rechargeable sodium ion secondary battery and a method for manufacturing the same, so as to solve the problems of the background art.
In order to achieve the purpose, the invention provides the following technical scheme: the utility model provides a chargeable sodium ion secondary battery of no negative pole, includes casing, diaphragm, positive pole piece and negative pole piece, the inside coiling of casing has diaphragm, positive pole piece and negative pole piece, and the diaphragm is located between positive pole piece and the negative pole piece.
A method for manufacturing a non-negative electrode rechargeable sodium ion secondary battery comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging;
in the first step, 80-95% of sodium-carbon coated sodium fast ion conductor material vanadium sodium phosphate positive electrode material, 1-5% of conductive agent, 1-5% of binder and 0.1-0.5% of dispersant are respectively selected according to the mass percentage of each component;
in the second step, the sodium fast ion conductor material vanadium sodium phosphate anode material coated with sodium carbon, the conductive agent, the binder and the dispersant selected in the first step are weighed according to the sum of the percentage of the components being 1, and then the weighed vanadium sodium phosphate anode material, the conductive agent, the binder and the dispersant are stirred and mixed to obtain anode slurry;
in the third step, the positive electrode slurry obtained in the second step is coated on a positive electrode current collector, the positive electrode current collector is made of aluminum foil or nickel foil, and then the positive electrode current collector house coated with the positive electrode slurry is baked in a baking oven;
in the fourth step, the positive current collector baked in the third step is placed under a rolling machine for rolling, then the rolled positive current collector is cut according to the required size, and then the cut positive current collector is subjected to sheet making treatment to obtain the required positive pole piece;
selecting a proper aluminum foil or nickel foil as a negative electrode material, and processing the selected negative electrode material by using a slicing and flaking process to obtain a negative electrode piece;
selecting a certain amount of solvent, electrolyte sodium salt and electrolyte additive, fully mixing and stirring the selected solvent, electrolyte sodium salt and electrolyte additive to prepare electrolyte, wherein the solvent content in the electrolyte is 40-60%, and the electrolyte additive comprises but is not limited to common film-forming additives of VC, PS, FEC, BP and CHB, and overcharge protection additive;
selecting a shell and a diaphragm with proper sizes for later use in the seventh step, stacking the positive pole piece obtained in the fourth step and the negative pole piece obtained in the fifth step, placing the diaphragm between the positive pole piece and the negative pole piece, winding the stacked diaphragm, the positive pole piece and the negative pole piece to obtain a wound material, and assembling the obtained wound material in the shell to obtain a semi-finished battery material;
in the eighth step, the electrolyte obtained in the sixth step is injected into the semi-finished battery material obtained in the seventh step, packaging is carried out to obtain a finished battery material, the obtained finished battery material is uniformly placed on the first inclined plate and stands for 2-3 hours, and when the inclined time is up, the finished battery material is placed on the second inclined plate and stands for 3-4 hours;
in the ninth step, the finished battery material obtained in the eighth step is charged to 0.65 of the electric quantity of the battery by using a 0.1C constant current, the time is required to be 6.5 hours, after standing for 20min, the battery material is discharged to 2.5V by using the 0.1C constant current, then the steps of circulating constant current charging and constant current discharging are carried out once, and meanwhile, sodium ions provided by a positive pole piece are deposited on a negative pole piece in the charging process to be used as a sodium source capable of charging and discharging;
in the tenth step, the finished battery material processed in the ninth step is charged to 4-4.2V, stored at normal temperature for 7-8 days, and then stored at 45-50 ℃ for 7-8 days to complete the aging process, after the aging process is completed, the voltage difference before and after the battery aging can be detected, and unqualified products are removed, so that the qualified products are finished products of the non-negative electrode rechargeable sodium ion secondary battery.
Preferably, in the sixth step, the non-aqueous electrolyte solution used as the solvent is prepared from the following aprotic organic solvents: n-methyl-2-pyrrolidone, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, vinylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, and ethyl propionate.
Preferably, in the sixth step, the ratio of sodium salt of electrolyte: sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium salt of sodium chloride which can be dissolved in the solvent, the electrolyte concentration is 0.5mol/L-2.0 mol/L; the electrolyte also needs to be added with 0.01-0.05mol/L lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate which can be dissolved in the solvent as additives.
Preferably, in the eighth step, the included angle between the first inclined plate and the horizontal plane is 45 °.
Preferably, in the eighth step, an included angle formed between the second inclined plate and the horizontal plane is 45 ° while an included angle formed between the first inclined plate and the second inclined plate is 90 °.
Preferably, in the step ten, the nominal capacity of the obtained non-negative electrode rechargeable sodium ion secondary battery is 4000 mAh.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares the sodium ion battery by using the material with the sodium fast ion conductor structure as the active substance, which is beneficial to large-scale application in the aspects of energy storage and power, improves the application range of the invention, simultaneously, in the preparation process, the finished battery material is placed at an inclined angle for placing treatment, which is beneficial to leading the electrolyte to be fully contacted with the pole piece, thereby improving the quality of the battery product, simultaneously, the negative pole piece of the battery product does not need the negative active material, the negative pole electrode uses an aluminum foil (net) or a nickel foil (net) as the negative pole piece, and the sodium ions provided by the positive pole material are deposited on the negative pole current collector as the sodium source capable of being charged and discharged in the charging process, thereby reducing the usage amount of the negative pole active material and reducing the preparation cost of the product.
Drawings
FIG. 1 is a cross-sectional view of the overall construction of the present invention;
FIG. 2 is an enlarged view of the structure of region A in FIG. 1;
fig. 3 is an XRD pattern of the positive electrode material in example 1 of the present invention;
fig. 4 is a charge-discharge diagram in the finished, non-negative electrode rechargeable sodium-ion secondary battery of example 1;
FIG. 5 is a flow chart of a method of the present invention;
in the figure: 1. a housing; 2. a diaphragm; 3. a positive electrode plate; 4. and (5) a negative pole piece.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, an embodiment of the present invention is shown: a non-negative electrode rechargeable sodium ion secondary battery comprises a shell 1, a diaphragm 2, a positive electrode plate 3 and a negative electrode plate 4, wherein the diaphragm 2, the positive electrode plate 3 and the negative electrode plate 4 are wound in the shell 1, and the diaphragm 2 is positioned between the positive electrode plate 3 and the negative electrode plate 4.
Referring to fig. 3-5, an embodiment of the present invention:
example 1:
a method for manufacturing a non-negative electrode rechargeable sodium ion secondary battery comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging;
in the first step, 90.5% of sodium-carbon coated sodium fast ion conductor material vanadium sodium phosphate positive electrode material, 4% of conductive agent, 5% of binder and 0.5% of dispersant are respectively selected according to the mass percentage of each component;
in the second step, the sodium fast ion conductor material vanadium sodium phosphate anode material coated with sodium carbon, the conductive agent, the binder and the dispersant selected in the first step are weighed according to the sum of the percentage of the components being 1, and then the weighed vanadium sodium phosphate anode material, the conductive agent, the binder and the dispersant are stirred and mixed to obtain anode slurry;
in the third step, the positive electrode slurry obtained in the second step is coated on a positive electrode current collector, the material of the positive electrode current collector is an aluminum foil (net) or a nickel foil (net), and then the positive electrode current collector house coated with the positive electrode slurry is baked in a baking oven;
in the fourth step, the positive current collector baked in the third step is placed under a rolling machine for rolling, then the rolled positive current collector is cut according to the required size, and then the cut positive current collector is subjected to sheet making treatment to obtain the required positive pole piece 3;
selecting a proper aluminum foil (net) or nickel foil (net) as a negative electrode material, and processing the selected negative electrode material by using a slicing and flaking process to obtain a negative electrode piece 4;
in the sixth step, a certain amount of solvent, electrolyte sodium salt and electrolyte additive are selected, then the selected solvent, electrolyte sodium salt and electrolyte additive are fully mixed and stirred to prepare electrolyte, the solvent content in the electrolyte is 40%, and the non-aqueous electrolyte solution used by the solvent is prepared from the following non-proton organic solvents: n-methyl-2-pyrrolidone, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, vinylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, and ethyl propionate, electrolyte sodium salt: sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium salt of sodium chloride soluble in the above-mentioned solvent, the electrolyte concentration is 0.5 mol/L; the electrolyte also needs to be added with 0.01mol/L lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate which can be dissolved in the solvent as additives, and the electrolyte additives include but are not limited to common film-forming additives of VC, PS, FEC, BP and CHB, and overcharge protection additives;
in the seventh step, a shell 1 and a diaphragm 2 with proper sizes are selected for standby, then the positive pole piece 3 obtained in the fourth step and the negative pole piece 4 obtained in the fifth step are stacked, the diaphragm 2 is placed between the positive pole piece 3 and the negative pole piece 4, then the stacked diaphragm 2, the positive pole piece 3 and the negative pole piece 4 are wound to obtain a wound material, and then the obtained wound material is assembled in the shell 1 to obtain a semi-finished battery material;
injecting the electrolyte obtained in the step six into the semi-finished product battery material obtained in the step seven, packaging to obtain a finished product battery material, uniformly placing the obtained finished product battery material on a first inclined plate, standing for 2 hours, wherein the included angle between the first inclined plate and the horizontal plane is 45 degrees, when the inclination time reaches, placing the finished product battery material on a second inclined plate, standing for 3 hours, the included angle between the second inclined plate and the horizontal plane is 45 degrees, and the included angle formed by the first inclined plate and the second inclined plate is 90 degrees;
in the ninth step, the finished battery material obtained in the eighth step is charged to 0.65 of the electric quantity of the battery by using a 0.1C constant current, the time is required to be 6.5h, after standing for 20min, the battery material is discharged to 2.5V by using the 0.1C constant current, then the steps of circulating constant current charging and constant current discharging are carried out once, and meanwhile, sodium ions provided by the positive pole piece 3 are deposited on the negative pole piece 4 in the charging process to be used as a sodium source capable of charging and discharging;
in the tenth step, the finished battery material processed in the ninth step is charged to 4V, stored at normal temperature for 7 days, and then stored at 45 ℃ for 7 days to complete the aging process, after the aging process is completed, the voltage difference before and after the battery aging can be detected, and then unqualified products are removed, so that the obtained qualified products are finished products of the non-negative electrode rechargeable sodium ion secondary battery, the obtained non-negative electrode rechargeable sodium ion secondary battery has the nominal capacity of 4000mAh, the XRD pattern of the positive electrode material in the finished product of the non-negative electrode rechargeable sodium ion secondary battery is shown in fig. 3, and the charge-discharge pattern in the finished product of the non-negative electrode rechargeable sodium ion secondary battery is shown in fig. 4.
Example 2:
a method for manufacturing a non-negative electrode rechargeable sodium ion secondary battery comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging;
in the first step, 91.5% of sodium-carbon-coated sodium fast ion conductor material vanadium sodium phosphate positive electrode material, 4% of conductive agent, 4% of binder and 0.5% of dispersant are respectively selected according to the mass percentage of each component;
in the second step, the sodium fast ion conductor material vanadium sodium phosphate anode material coated with sodium carbon, the conductive agent, the binder and the dispersant selected in the first step are weighed according to the sum of the percentage of the components being 1, and then the weighed vanadium sodium phosphate anode material, the conductive agent, the binder and the dispersant are stirred and mixed to obtain anode slurry;
in the third step, the positive electrode slurry obtained in the second step is coated on a positive electrode current collector, the material of the positive electrode current collector is an aluminum foil (net) or a nickel foil (net), and then the positive electrode current collector house coated with the positive electrode slurry is baked in a baking oven;
in the fourth step, the positive current collector baked in the third step is placed under a rolling machine for rolling, then the rolled positive current collector is cut according to the required size, and then the cut positive current collector is subjected to sheet making treatment to obtain the required positive pole piece 3;
selecting a proper aluminum foil (net) or nickel foil (net) as a negative electrode material, and processing the selected negative electrode material by using a slicing and flaking process to obtain a negative electrode piece 4;
in the sixth step, a certain amount of solvent, electrolyte sodium salt and electrolyte additive are selected, then the selected solvent, electrolyte sodium salt and electrolyte additive are fully mixed and stirred to prepare electrolyte, the solvent content in the electrolyte is 40%, and the non-aqueous electrolyte solution used by the solvent is prepared from the following non-proton organic solvents: n-methyl-2-pyrrolidone, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, vinylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, and ethyl propionate, electrolyte sodium salt: sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium salt of sodium chloride soluble in the above-mentioned solvent, the electrolyte concentration is 0.5 mol/L; the electrolyte also needs to be added with 0.01 lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate which can be dissolved in the solvent as additives, and the electrolyte additives include but are not limited to film-forming additives and overcharge protection additives commonly used by VC, PS, FEC, BP and CHB;
in the seventh step, a shell 1 and a diaphragm 2 with proper sizes are selected for standby, then the positive pole piece 3 obtained in the fourth step and the negative pole piece 4 obtained in the fifth step are stacked, the diaphragm 2 is placed between the positive pole piece 3 and the negative pole piece 4, then the stacked diaphragm 2, the positive pole piece 3 and the negative pole piece 4 are wound to obtain a wound material, and then the obtained wound material is assembled in the shell 1 to obtain a semi-finished battery material;
injecting the electrolyte obtained in the step six into the semi-finished product battery material obtained in the step seven, packaging to obtain a finished product battery material, uniformly placing the obtained finished product battery material on a first inclined plate, standing for 2 hours, wherein the included angle between the first inclined plate and the horizontal plane is 45 degrees, when the inclination time reaches, placing the finished product battery material on a second inclined plate, standing for 3 hours, the included angle between the second inclined plate and the horizontal plane is 45 degrees, and the included angle formed by the first inclined plate and the second inclined plate is 90 degrees;
in the ninth step, the finished battery material obtained in the eighth step is charged to 0.65 of the electric quantity of the battery by using a 0.1C constant current, the time is required to be 6.5h, after standing for 20min, the battery material is discharged to 2.5V by using the 0.1C constant current, then the steps of circulating constant current charging and constant current discharging are carried out once, and meanwhile, sodium ions provided by the positive pole piece 3 are deposited on the negative pole piece 4 in the charging process to be used as a sodium source capable of charging and discharging;
in the tenth step, the finished battery material processed in the ninth step is charged to 4V, stored at normal temperature for 7 days, and then stored at 45 ℃ for 7 days to complete the aging process, after the aging process is completed, the voltage difference before and after the battery aging can be detected, unqualified products are removed, the obtained qualified products are finished products of the non-negative electrode rechargeable sodium ion secondary battery, and the nominal capacity of the obtained non-negative electrode rechargeable sodium ion secondary battery is 4000 mAh.
Example 3:
a method for manufacturing a non-negative electrode rechargeable sodium ion secondary battery comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging;
in the first step, 92.5% of sodium-carbon coated sodium fast ion conductor material vanadium sodium phosphate positive electrode material, 3% of conductive agent, 4% of binder and 0.5% of dispersant are respectively selected according to the mass percentage of each component;
in the second step, the sodium fast ion conductor material vanadium sodium phosphate anode material coated with sodium carbon, the conductive agent, the binder and the dispersant selected in the first step are weighed according to the sum of the percentage of the components being 1, and then the weighed vanadium sodium phosphate anode material, the conductive agent, the binder and the dispersant are stirred and mixed to obtain anode slurry;
in the third step, the positive electrode slurry obtained in the second step is coated on a positive electrode current collector, the material of the positive electrode current collector is an aluminum foil (net) or a nickel foil (net), and then the positive electrode current collector house coated with the positive electrode slurry is baked in a baking oven;
in the fourth step, the positive current collector baked in the third step is placed under a rolling machine for rolling, then the rolled positive current collector is cut according to the required size, and then the cut positive current collector is subjected to sheet making treatment to obtain the required positive pole piece 3;
selecting a proper aluminum foil (net) or nickel foil (net) as a negative electrode material, and processing the selected negative electrode material by using a slicing and flaking process to obtain a negative electrode piece 4;
in the sixth step, a certain amount of solvent, electrolyte sodium salt and electrolyte additive are selected, then the selected solvent, electrolyte sodium salt and electrolyte additive are fully mixed and stirred to prepare electrolyte, the solvent content in the electrolyte is 40%, and the non-aqueous electrolyte solution used by the solvent is prepared from the following non-proton organic solvents: n-methyl-2-pyrrolidone, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, vinylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, and ethyl propionate, electrolyte sodium salt: sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium salt of sodium chloride soluble in the above-mentioned solvent, the electrolyte concentration is 0.5 mol/L; the electrolyte also needs to be added with 0.01mol/L lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate which can be dissolved in the solvent as additives, and the electrolyte additives include but are not limited to common film-forming additives of VC, PS, FEC, BP and CHB, and overcharge protection additives;
in the seventh step, a shell 1 and a diaphragm 2 with proper sizes are selected for standby, then the positive pole piece 3 obtained in the fourth step and the negative pole piece 4 obtained in the fifth step are stacked, the diaphragm 2 is placed between the positive pole piece 3 and the negative pole piece 4, then the stacked diaphragm 2, the positive pole piece 3 and the negative pole piece 4 are wound to obtain a wound material, and then the obtained wound material is assembled in the shell 1 to obtain a semi-finished battery material;
injecting the electrolyte obtained in the step six into the semi-finished product battery material obtained in the step seven, packaging to obtain a finished product battery material, uniformly placing the obtained finished product battery material on a first inclined plate, standing for 2 hours, wherein the included angle between the first inclined plate and the horizontal plane is 45 degrees, when the inclination time reaches, placing the finished product battery material on a second inclined plate, standing for 3 hours, the included angle between the second inclined plate and the horizontal plane is 45 degrees, and the included angle formed by the first inclined plate and the second inclined plate is 90 degrees;
in the ninth step, the finished battery material obtained in the eighth step is charged to 0.65 of the electric quantity of the battery by using a 0.1C constant current, the time is required to be 6.5h, after standing for 20min, the battery material is discharged to 2.5V by using the 0.1C constant current, then the steps of circulating constant current charging and constant current discharging are carried out once, and meanwhile, sodium ions provided by the positive pole piece 3 are deposited on the negative pole piece 4 in the charging process to be used as a sodium source capable of charging and discharging;
in the tenth step, the finished battery material processed in the ninth step is charged to 4V, stored at normal temperature for 7 days, and then stored at 45 ℃ for 7 days to complete the aging process, after the aging process is completed, the voltage difference before and after the battery aging can be detected, unqualified products are removed, the obtained qualified products are finished products of the non-negative electrode rechargeable sodium ion secondary battery, and the nominal capacity of the obtained non-negative electrode rechargeable sodium ion secondary battery is 4000 mAh.
After the finished product of the non-negative electrode rechargeable sodium ion secondary battery obtained in the above embodiment is respectively charged and discharged for 100 times in a circulating way, the capacity retention rate of the battery is measured, and the obtained results are as follows:
| capacity retention ratio% | |
| Example 1 | 98.1％ |
| Example 2 | 97.4％ |
| Example 3 | 97.8％ |
Based on the above, in the invention, the material of the negative electrode plate 4 is aluminum foil (mesh) or nickel foil (mesh), and sodium ions provided by the positive electrode material are deposited on the negative electrode current collector as a sodium source capable of charging and discharging in the charging process, so that the use of the negative electrode active material is avoided, the production cost for preparing the battery product is reduced, meanwhile, the material with the sodium fast ion conductor structure is used as the positive electrode active material, the material is beneficial to being applied to the aspects of energy storage and power in a large scale, the application range of the invention is improved, and meanwhile, in the preparation process, the finished battery material is placed at an inclined angle for placing treatment, so that the electrolyte is beneficial to being fully contacted with the electrode plate, and the quality of the battery product is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The utility model provides a but, there is not negative pole rechargeable sodium ion secondary battery, includes casing (1), diaphragm (2), positive pole piece (3) and negative pole piece (4), its characterized in that: the diaphragm (2), the positive pole piece (3) and the negative pole piece (4) are wound in the shell (1), and the diaphragm (2) is located between the positive pole piece (3) and the negative pole piece (4).
2. A method for manufacturing a non-negative electrode rechargeable sodium ion secondary battery comprises the following steps of selecting raw materials; step two, batching; step three, baking; step four, rolling; step five, slitting; step six, preparation; step seven, assembling; step eight, injecting liquid; step nine, formation; step ten, aging; the method is characterized in that:
in the first step, 80-95% of sodium-carbon coated sodium fast ion conductor material vanadium sodium phosphate positive electrode material, 1-5% of conductive agent, 1-5% of binder and 0.1-0.5% of dispersant are respectively selected according to the mass percentage of each component;
in the second step, the sodium fast ion conductor material vanadium sodium phosphate anode material coated with sodium carbon, the conductive agent, the binder and the dispersant selected in the first step are weighed according to the sum of the percentage of the components being 1, and then the weighed vanadium sodium phosphate anode material, the conductive agent, the binder and the dispersant are stirred and mixed to obtain anode slurry;
in the third step, the positive electrode slurry obtained in the second step is coated on a positive electrode current collector, the material of the positive electrode current collector is an aluminum foil (net) or a nickel foil (net), and then the positive electrode current collector house coated with the positive electrode slurry is baked in a baking oven;
in the fourth step, the positive current collector baked in the third step is placed under a rolling machine for rolling, then the rolled positive current collector is cut according to the required size, and then the cut positive current collector is subjected to sheet making treatment to obtain the required positive pole piece (3);
selecting a proper aluminum foil (net) or nickel foil (net) as a negative electrode material, and processing the selected negative electrode material by using a slicing and flaking process to obtain a negative electrode piece (4);
selecting a certain amount of solvent, electrolyte sodium salt and electrolyte additive, fully mixing and stirring the selected solvent, electrolyte sodium salt and electrolyte additive to prepare electrolyte, wherein the solvent content in the electrolyte is 40-60%, and the electrolyte additive comprises but is not limited to common film-forming additives of VC, PS, FEC, BP and CHB, and overcharge protection additive;
in the seventh step, a shell (1) and a diaphragm (2) with proper sizes are selected for standby, then the positive pole piece (3) obtained in the fourth step and the negative pole piece (4) obtained in the fifth step are stacked, the diaphragm (2) is placed between the positive pole piece (3) and the negative pole piece (4), then the stacked diaphragm (2), the positive pole piece (3) and the negative pole piece (4) are wound to obtain a wound material, and then the obtained wound material is assembled in the shell (1) to obtain a semi-finished battery material;
in the eighth step, the electrolyte obtained in the sixth step is injected into the semi-finished battery material obtained in the seventh step, packaging is carried out to obtain a finished battery material, the obtained finished battery material is uniformly placed on the first inclined plate and stands for 2-3 hours, and when the inclined time is up, the finished battery material is placed on the second inclined plate and stands for 3-4 hours;
in the ninth step, the finished battery material obtained in the eighth step is charged to 0.65 of the electric quantity of the battery by using a 0.1C constant current, the time is required to be 6.5h, after standing for 20min, the battery material is discharged to 2.5V by using the 0.1C constant current, then the steps of circulating constant current charging and constant current discharging are carried out once, and meanwhile, sodium ions provided by the positive pole piece (3) are deposited on the negative pole piece (4) in the charging process to serve as a sodium source capable of charging and discharging;
in the tenth step, the finished battery material processed in the ninth step is charged to 4-4.2V, stored at normal temperature for 7-8 days, and then stored at 45-50 ℃ for 7-8 days to complete the aging process, after the aging process is completed, the voltage difference before and after the battery aging can be detected, and unqualified products are removed, so that the qualified products are finished products of the non-negative electrode rechargeable sodium ion secondary battery.
3. The method of claim 2, wherein the method comprises: in the sixth step, the non-aqueous electrolyte solution used as the solvent is prepared from the following aprotic organic solvents: n-methyl-2-pyrrolidone, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, vinylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, and ethyl propionate.
4. The method of claim 2, wherein the method comprises: in the sixth step, the sodium salt of the electrolyte: sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium salt of sodium chloride which can be dissolved in the solvent, the electrolyte concentration is 0.5mol/L-2.0 mol/L; the electrolyte also needs to be added with 0.01-0.05mol/L lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate which can be dissolved in the solvent as additives.
5. The method of claim 2, wherein the method comprises: in the eighth step, an included angle between the first inclined plate and the horizontal plane is 45 °.
6. The method of claim 2, wherein the method comprises: in the eighth step, the included angle between the second inclined plate and the horizontal plane is 45 degrees, and the included angle formed by the first inclined plate and the second inclined plate is 90 degrees.
7. The method of claim 2, wherein the method comprises: in the step ten, the nominal capacity of the obtained non-negative electrode rechargeable sodium ion secondary battery is 4000 mAh.
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| CN114583174A (en) * | 2022-03-21 | 2022-06-03 | 蜂巢能源科技股份有限公司 | Sodium ion battery and preparation method thereof |
| CN116264323A (en) * | 2021-12-15 | 2023-06-16 | 张家港市国泰华荣化工新材料有限公司 | Sodium ion battery electrolyte and sodium ion battery |
| CN117175016A (en) * | 2023-09-21 | 2023-12-05 | 北京希倍动力科技有限公司 | Negative-electrode-free sodium ion secondary battery, electrolyte and application thereof |
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| FR2961634B1 (en) * | 2010-06-17 | 2013-02-15 | Centre Nat Rech Scient | PROCESS FOR THE PRODUCTION OF A LITHIUM OR SODIUM BATTERY |
| CN107148697A (en) * | 2015-12-30 | 2017-09-08 | 深圳先进技术研究院 | A kind of new sodium-ion battery and preparation method thereof |
| CN109155415A (en) * | 2016-05-06 | 2019-01-04 | 深圳中科瑞能实业有限公司 | A kind of sodium-ion battery and preparation method thereof |
| CN106876781A (en) * | 2017-03-10 | 2017-06-20 | 欣旺达电子股份有限公司 | Sodium-ion battery and preparation method thereof |
| CN108336301A (en) * | 2018-02-06 | 2018-07-27 | 哈尔滨工业大学 | A kind of high-performance sodium-ion battery cathode and preparation method thereof |
| CN110429329A (en) * | 2019-08-15 | 2019-11-08 | 湖南立方新能源科技有限责任公司 | A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery |
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| CN116264323A (en) * | 2021-12-15 | 2023-06-16 | 张家港市国泰华荣化工新材料有限公司 | Sodium ion battery electrolyte and sodium ion battery |
| CN116264323B (en) * | 2021-12-15 | 2024-03-01 | 张家港市国泰华荣化工新材料有限公司 | Sodium ion battery electrolyte and sodium ion battery |
| CN114583174A (en) * | 2022-03-21 | 2022-06-03 | 蜂巢能源科技股份有限公司 | Sodium ion battery and preparation method thereof |
| CN114583174B (en) * | 2022-03-21 | 2024-03-26 | 蜂巢能源科技股份有限公司 | Sodium ion battery and preparation method thereof |
| CN117175016A (en) * | 2023-09-21 | 2023-12-05 | 北京希倍动力科技有限公司 | Negative-electrode-free sodium ion secondary battery, electrolyte and application thereof |
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