CN115275208B - High-specific-energy aqueous lithium ion battery and preparation method thereof - Google Patents
High-specific-energy aqueous lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high specific energy water system lithium ion battery and a preparation method thereof. One or more hydrogen evolution inhibitors are mixed and added into an aqueous solution dissolved with lithium salt, so that the electrochemical stability window of the electrolyte is expanded, and the demand of the lithium salt is reduced, so that a high-energy density water-based lithium ion battery is possible. Therefore, the problems of narrow electrochemical window, low energy density of the battery and high cost of the electrolyte are solved, and the selection of electrode materials is more diversified. Adding hydrogen evolution inhibitors such as acetoacetic acid, 3-sulfolene, diethyl sulfone, 2,2-sulfonyl diethanol and the like into a water solution in which lithium salt is dissolved to obtain an aqueous electrolyte; and coating an artificial solid electrolyte interface layer rich in lithium carbonate on the surfaces of the positive and negative electrode materials by a supercritical carbon dioxide method.
Description
Technical Field
The invention relates to the field of chemical power sources of lithium ion batteries, in particular to a high-specific energy aqueous lithium ion battery and a preparation method thereof.
Background
At present, lithium ion batteries have become more and more important in people's daily life, and gradually become an indispensable important tool for people to eat and live. However, the problems of the lithium ion battery are gradually reported, and particularly, the safety problem is highlighted. Because the lithium ion battery mainly uses organic electrolyte at present, dangerous accidents such as fire and even explosion are easy to occur when short circuit occurs. On the contrary, the aqueous lithium ion battery using the aqueous solution as the electrolyte fundamentally solves the problem, and compared with the organic lithium ion battery, the aqueous lithium ion battery is safer and has lower cost.
However, since the thermodynamic stability window of water is narrow and is only 1.23V in total, many choices of anode and cathode materials for the aqueous lithium ion battery are greatly limited, particularly on the negative electrode side, hydrogen evolution easily occurs, and some low-potential negative electrode materials (such as Li4Ti5O 12) cannot be used in the aqueous lithium ion battery. Therefore, the energy density of the water-based lithium ion battery is very low (less than 70Wh kg < -1 >), and the output voltage is also very low, so that the development and the application of the water-based lithium ion battery are greatly limited.
It is therefore very important to widen the electrochemical window of the aqueous electrolyte. In non-patent literature Science (2015, 350 (6263): 938-943), suo et al reported a "water in salt" electrolyte that had an electrochemical window widened to 3.0V by the addition of ultra-high concentration of lithium salt at salt concentration of 21mol/kg in 2015. However, with the widening of the electrochemical window, the salt concentration of the aqueous electrolyte is too high, the viscosity is large, the ionic conductivity is reduced, the cost is too high, and the aqueous electrolyte cannot be used on a large scale.
Therefore, how to widen the electrochemical window and ensure that the cost cannot be too high is a problem which needs to be solved intensively at present.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high specific energy aqueous lithium ion battery and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the high specific energy water-based lithium ion battery comprises a positive electrode current collector, a negative electrode current collector, a positive electrode material, a negative electrode material, a diaphragm, a water-based electrolyte and a shell, wherein the water-based electrolyte contains water, lithium salt and a hydrogen evolution inhibitor, and the surfaces of the positive electrode material and the negative electrode material are coated with lithium carbonate. One or more hydrogen evolution inhibitors are mixed and added into an aqueous solution dissolved with lithium salt, so that the electrochemical stability window of the electrolyte is expanded, and the demand of the lithium salt is reduced, so that a high-energy density water-based lithium ion battery is possible. Therefore, the problems of narrow electrochemical window, low battery energy density and high electrolyte cost are solved, and the selection of electrode materials is more diversified.
Preferably, the hydrogen evolution inhibitor is one or more of acetoacetate, 3-sulfolene, diethylsulfone, 2,2-sulfonyldiethanol, 1,3 dioxane, or combinations thereof.
Preferably, the lithium salt is at least one of lithium perchlorate, lithium nitrate, lithium sulfate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (pentafluoroethylsulfonyl) imide.
Preferably, the mass ratio of the hydrogen evolution inhibitor to the lithium salt is 2~7:8~3.
Preferably, the content of water in the aqueous electrolyte is 5% to 30% of the sum of the masses of the lithium salt and the hydrogen evolution inhibitor.
Preferably, the positive electrode current collector is selected from a titanium foil, a stainless steel foil or a carbon paper, and the negative electrode current collector is selected from an aluminum foil or a stainless steel foil.
Preferably, the separator is one selected from glass fiber, polypropylene and cellulose; the positive electrode material is lithium manganate (LiMn) 2 O 4 ) Lithium iron phosphate (LiFePO) 4 ) Lithium nickel manganese oxide (LiNi) 0.5 Mn 1.5 O).
Preferably, the negative electrode material is titanium niobium oxide (TiNb) 2 O 7 ) Lithium titanate (Li) 4 Ti 5 O 12 ) Molybdenum disulfide (MoS) 2 ) Titanium disulfide (TiS) 2 ) Sulfur (S), titanium dioxide (TiO) 2 ) One kind of (1).
Preferably, the positive electrode material and the negative electrode material are coated with lithium carbonate (Li) having a thickness of 1 to 50 nm by the supercritical carbon dioxide method 2 CO 3 ) And (4) coating.
A preparation method of a high specific energy water-based lithium ion battery, a coating of lithium carbonate (Li 2CO 3) by a supercritical carbon dioxide method comprises the following steps:
(1) Mixing the anode material or the cathode material with LiOH accounting for 1% -10% of the weight of the anode material or the cathode material, dispersing the mixture in deionized water, freezing the obtained dispersion liquid by using liquid nitrogen or a refrigerator, putting the frozen dispersion liquid into a freeze dryer, and vacuumizing and drying the frozen dispersion liquid for 12-48 hours to completely remove the solvent to obtain mixed powder;
(2) Grinding and crushing the obtained powder, then filling the powder into a supercritical carbon dioxide reaction device, vacuumizing the supercritical carbon dioxide reaction device, and then introducing carbon dioxide gas, wherein the pressure is controlled to be 7 to 25MPa, the temperature is controlled to be 33 to 60 ℃, and the temperature is kept for 6 to 24 hours;
(3) And releasing the gas in the reaction device to obtain the anode material or the cathode material coated with a 1-50 nanometer thick lithium carbonate (Li 2CO 3) coating.
The invention has the beneficial effects that:
1. the novel electrolyte is obtained by adding the hydrogen evolution inhibitor into an aqueous solution in which a lithium salt is dissolved. Firstly, the lithium salt is less in dosage, the hydrogen evolution inhibitor mainly acts, inhibitor molecules and water molecules form strong hydrogen bonds, the original hydrogen bond network is broken, the inhibitor molecules are used as crowding agents, and free water molecules are limited in the network by long chains of the inhibitor molecules; meanwhile, the primary solvation sheath of the lithium ions is changed, the lithium ions in the lithium ion solvation sheath are surrounded by four water molecules before the hydrogen evolution inhibitor is added, the hydrogen evolution reaction is easy to occur, and the inhibitor and the anions of the lithium salt can enter the primary solvation sheath of the lithium ions after the hydrogen evolution inhibitor is added to form a new solvation structure; on the other hand, the combined action of the anion of the lithium salt and the hydrogen evolution inhibitor can participate in the SEI structure at the interface of the negative electrode, and the main components are LiF and Li 2 CO 3 Etc., the formation of SEI can further prevent the generation of hydrogen evolution reaction. Under the comprehensive influence of the factors, the electrochemical window of the electrolyte is further widened, the hydrogen evolution reaction is effectively inhibited, and more importantly, the hydrogen evolution reaction is reducedThe dosage of lithium salt is increased, and the cost of the electrolyte is greatly reduced. Can match with a high-energy-density water system lithium ion battery;
2. in the invention, the proportion of the hydrogen evolution inhibitor (acetoacetic acid, 3-sulfolene, diethylsulfone, 2,2-sulfonyl diethanol, 1,4 dioxane) is controlled between 5~7 parts, and the titanium niobium oxygen material can stably work and the hydrogen evolution reaction is inhibited corresponding to 3 parts of lithium salt. If the lithium salt is excessive, the viscosity of the electrolyte is too high, the ionic conductivity is reduced, and the energy density of the battery is reduced; if the lithium salt is too little, the electrochemical window is narrow, the hydrogen evolution phenomenon is obvious, and the negative electrode material has no way to work stably;
3. according to the water-based lithium ion battery, the positive electrode material is one of lithium manganate, lithium iron phosphate and lithium nickel manganese oxide, and the negative electrode material is one of titanium niobium oxide, lithium titanate, molybdenum disulfide, titanium disulfide, sulfur and titanium dioxide. Solves the problem of high potential anode material (lithium nickel manganese 4.7V vs Li) in the aqueous lithium ion battery + Li) and low potential cathode material (Ti-Nb-O1.6V vs Li) + /Li) case of not working properly;
4. the water system lithium ion battery disclosed by the invention adopts a supercritical carbon dioxide method to coat the artificial solid electrolyte interface layer rich in lithium carbonate on the surfaces of the positive and negative electrode materials, so that the water system lithium ion battery with high specific energy is realized.
Drawings
FIG. 1 is a window of electrochemical stability measured by linear sweep voltammetry of example one;
FIG. 2 shows lithium manganate (LiMn) as an example I 2 O 4 ) And TiNb oxide (TiNb) 2 O 7 ) The charge and discharge performance of the aqueous lithium ion full cell as the positive and negative electrode materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described with reference to the accompanying drawings and embodiments:
the first embodiment is as follows:
to 10 parts of 1,4-dioxane was added 2 parts of bis (trifluoromethylsulfonyl) imideAdding 10 parts of deionized water to prepare solution, and carrying out N 2 After bubbling treatment for 20min, fully stirring at 30 ℃ until the water-based electrolyte is completely dissolved to obtain the water-based electrolyte. Electrochemical measurements of the electrolyte were performed according to linear sweep voltammetry, resulting in an electrochemical stability window of approximately 2V, as shown in figure 1.
With lithium manganate (LiMn) 2 O 4 ) And TiNb oxide (TiNb) 2 O 7 ) Respectively used as the positive electrode material and the negative electrode material of the water-based lithium ion battery. Respectively mixing the anode and cathode materials with LiOH accounting for 5% of the mass of the anode and cathode materials, freeze-drying, introducing CO under the conditions that the pressure is 7.2MPa and the temperature is 33 DEG C 2 Performing supercritical reaction, and obtaining Li with the thickness of about 10 nanometers after 24 hours 2 CO 3 And (3) a layer. According to the active materials of the anode and cathode materials: conductive agent: weighing corresponding substances according to the mass ratio of 8.
And (3) assembling the electrode plates and the prepared aqueous electrolyte into a CR2032 type battery by using glass fibers as a diaphragm, standing overnight, and then carrying out charge and discharge tests on the battery. The charging and discharging voltage range is 0.8-2.8V, and the charging and discharging are carried out at 0.1C. The specific energy of the cell was 198 watt-hours per kilogram.
Example two:
and adding water and lithium salt into the 3-sulfolene serving as a hydrogen evolution inhibitor to prepare an electrolyte. Adding 5 parts, 6 parts and 7 parts of 3-sulfolene to 8 parts of water, respectively, and then adding 3 parts of lithium hexafluorophosphate in the presence of N 2 Stirring vigorously under atmosphere until the water-system electrolytes with different concentrations are completely dissolved. Electrochemical tests of the electrolyte according to a linear sweep voltammetry method all obtained an electrochemical stability window of about 1.8V.
Lithium iron phosphate and molybdenum disulfide are respectively used as a positive electrode material and a negative electrode material of the aqueous lithium ion battery. Respectively mixing the anode and cathode materials with LiOH accounting for 7% of the mass of the anode and cathode materials, freeze-drying the mixture, and introducing CO under the conditions that the pressure is 8MPa and the temperature is 35 DEG C 2 Carrying out supercritical reaction, obtaining large product after 12hAbout 3 nm thick Li 2 CO 3 And (3) a layer. According to the active materials of the anode and cathode materials: conductive agent: weighing corresponding substances according to the mass ratio of the binder of 8.
And (3) assembling the electrode plate and the prepared aqueous electrolyte into a CR2032 type battery by using polypropylene as a diaphragm, standing overnight, and then carrying out charge and discharge tests on the battery. The charging and discharging voltage range is 0.6-2.7V, and the charging and discharging are carried out at 0.1C. The specific energy of the battery is 120 watt-hours per kilogram.
Example three:
5 parts of 2,2-sulfonyl diethanol and 8 parts of water are mixed, then 3 parts of lithium perchlorate is added to prepare a solution, and the solution is added into N 2 And (3) stirring vigorously at 30 ℃ in the atmosphere until the water-based electrolyte is completely dissolved to obtain the water-based electrolyte. And performing electrochemical test on the electrolyte according to a linear sweep voltammetry method to obtain an electrochemical stability window of 1.5V.
Lithium manganate and titanium disulfide are respectively used as a positive electrode material and a negative electrode material of the aqueous lithium ion battery. Respectively mixing the anode and cathode materials with LiOH with the mass of 9 percent of the anode and cathode materials, freeze-drying, and introducing CO under the conditions that the pressure is 10MPa and the temperature is 40 DEG 2 Performing supercritical reaction, and obtaining Li with the thickness of about 6 nanometers after 10 hours 2 CO 3 And (3) a layer. According to the active materials of the anode and cathode materials: conductive agent: weighing corresponding substances according to the mass ratio of the binder of 8.
The electrode sheet and the prepared aqueous electrolyte are assembled into a CR2032 type battery by taking cellulose as a diaphragm, the battery is kept still for one night, and then the battery is subjected to charge and discharge tests. The charging and discharging voltage range is 0.7-2.7V, and the charging and discharging are carried out at 0.1C. The specific energy of the cell was 148 watt-hours per kilogram.
Example four:
diethyl sulfone, water and lithium salt are used as the ingredientsTo this, 6 parts of diethyl sulfone are added to 8 parts of water, and 2 parts of lithium sulfate are added, in N 2 Stirring the mixture under the atmosphere until the mixture is completely dissolved to obtain the water-based electrolyte. And performing electrochemical test on the electrolyte according to a linear sweep voltammetry method to obtain an electrochemical stability window of 1.5V. Lithium manganate and titanium disulfide are respectively used as the anode material and the cathode material of the aqueous lithium ion battery. Respectively mixing the anode material and the cathode material with LiOH accounting for 10% of the mass of the anode material and the cathode material, freezing and drying the mixture, and introducing CO under the conditions that the pressure is 8.5MPa and the temperature is 50 DEG C 2 Carrying out supercritical reaction, and obtaining Li with the thickness of about 8 nanometers after 7 hours 2 CO 3 And (3) a layer. According to the active substance: conductive agent: weighing corresponding substances according to the mass ratio of 8 to 1 of the binder, adding a proper amount of N-methylpyrrolidone (NMP) as a solvent, preparing slurry, coating the slurry on an aluminum foil, drying the aluminum foil in a vacuum oven at 80 ℃ for 24 hours,
the electrode sheet and the prepared aqueous electrolyte are assembled into a CR2032 type battery by taking glass fiber as a diaphragm, the battery is kept still for one night, and then the battery is subjected to charge and discharge tests. The charging and discharging voltage range is 1.0-2.5V, and the charging and discharging are carried out at 0.1C. The specific energy of the battery was 130 watt-hours per kilogram.
Example five:
adding 3 parts of tetrahydrofurfuryl alcohol to 5 parts of 3-sulfolene, adding 8 parts of water and 3 parts of lithium tetrafluoroborate to prepare a solution, and adding the solution to a reactor 2 And fully stirring at 30 ℃ in the atmosphere until the solution is completely dissolved to obtain the water-based electrolyte. And performing electrochemical test on the electrolyte according to a linear sweep voltammetry method to obtain an electrochemical stability window of 1.7V.
The lithium nickel manganese oxide and the titanium dioxide are respectively used as a positive electrode material and a negative electrode material of the aqueous lithium ion battery. Respectively mixing the anode and cathode materials with LiOH accounting for 2% of the mass of the anode and cathode materials, freeze-drying, and introducing CO under the conditions that the pressure is 8.6MPa and the temperature is 43 DEG C 2 Performing supercritical reaction to obtain Li with the thickness of about 15 nanometers after 30 hours 2 CO 3 And (3) a layer. According to the active substance: conductive agent: weighing corresponding substances according to the mass ratio of 8And transferring to a vacuum drying oven at 80 ℃ for baking for 24h.
The electrode sheet and the prepared aqueous electrolyte are assembled into a CR2032 type battery by taking glass fiber as a diaphragm, the battery is kept still for one night, and then the battery is subjected to charge and discharge tests. The charging and discharging voltage range is 1-2.6V, and the charging and discharging are carried out at 0.1C. The specific energy of the cell was 158 watt-hours per kilogram.
Example six:
adding 3 parts of tetrahydrofurfuryl alcohol to 5 parts of diethyl sulfone, adding 8 parts of water and 3 parts of lithium nitrate to prepare a solution, and reacting under N 2 And fully stirring at 30 ℃ in the atmosphere until the electrolyte is completely dissolved to obtain the aqueous electrolyte. And performing electrochemical test on the electrolyte according to a linear sweep voltammetry method to obtain an electrochemical stability window of 1.6V.
Lithium manganate and lithium titanate are respectively used as a positive electrode material and a negative electrode material of the aqueous lithium ion battery. Respectively mixing the anode and cathode materials with LiOH accounting for 9% of the mass of the anode and cathode materials, freeze-drying, and introducing CO under the conditions that the pressure is 9.1MPa and the temperature is 45 DEG C 2 Performing supercritical reaction, and obtaining Li with the thickness of about 20 nanometers after 35 hours 2 CO 3 And (3) a layer. According to the active substance: conductive agent: the mass ratio of the binder is 8.
And (3) assembling the electrodes into a CR2032 type battery by using glass fibers as a diaphragm, adding the electrolyte, standing overnight, and then carrying out charge and discharge tests on the battery. The charging and discharging voltage range is 1.1-2.5V, and the charging and discharging are carried out at 0.1C. The specific energy of the battery was 135 watt-hours per kilogram.
Seven control groups:
2 parts of lithium perchlorate are added to 8 parts of water in N 2 And fully stirring at 30 ℃ in the atmosphere until the electrolyte is completely dissolved to obtain the aqueous electrolyte. And performing electrochemical test on the electrolyte according to a linear sweep voltammetry method to obtain an electrochemical stability window of 1.3V.
Lithium manganate and titanium disulfide are respectively used as a positive electrode material and a negative electrode material of the aqueous lithium ion battery. According to the active substance: conductive agent: the mass ratio of the binder is 8.
And (3) assembling the electrodes into a CR2032 type battery by using glass fibers as a diaphragm, adding the electrolyte, standing overnight, and then carrying out charge and discharge tests on the battery. The charging and discharging voltage range is 0.5-1.8V, and the charging and discharging are carried out at 0.1C. The specific energy of the battery is 30 watt-hours per kilogram.
The electrochemical windows and specific energies of aqueous lithium ions for the electrolytes of examples one through six and control group seven are as follows:
from the data in the table, after the hydrogen evolution inhibitor is added, the electrochemical window of the aqueous electrolyte is remarkably widened to be more than 1.5V, and the aqueous electrolyte can be matched with lithium titanate and other negative electrode materials with lower lithium intercalation potential to form an aqueous lithium ion battery with higher voltage. And, by using supercritical CO 2 Reaction method for coating Li-rich surface of positive and negative electrode 2 CO 3 The artificial solid electrolyte interface layer of (3) can preferably suppress side reactions on the electrode surface. Therefore, the formed aqueous lithium ion battery has higher specific energy and better cycle stability.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A high specific energy water system lithium ion battery comprises a shell, a positive current collector, a negative current collector, a positive material, a negative material, a diaphragm and a water system electrolyte, and is characterized in that:
the water system electrolyte contains water, lithium salt and a hydrogen evolution inhibitor, and the surfaces of the positive electrode material and the negative electrode material are coated with lithium carbonate;
the hydrogen evolution inhibitor is one or more of 3-sulfolene, diethyl sulfone, 2,2-sulfonyl diethanol, 1,3 dioxane;
the positive electrode material is one of lithium manganate, lithium iron phosphate and lithium nickel manganese; the negative electrode material is one of titanium niobium oxide, lithium titanate, molybdenum disulfide, titanium disulfide and titanium dioxide;
the positive electrode material and the negative electrode material are coated with a lithium carbonate coating with the thickness of 1-50 nanometers by adopting a supercritical carbon dioxide method;
the method for coating the lithium carbonate coating by the supercritical carbon dioxide method comprises the following steps:
(1) Mixing the anode material or the cathode material with LiOH accounting for 1% -10% of the weight of the anode material or the cathode material, dispersing the mixture in deionized water, freezing the obtained dispersion liquid by using liquid nitrogen or a refrigerator, putting the frozen dispersion liquid into a freeze dryer, and vacuumizing and drying the frozen dispersion liquid for 12-48 hours to completely remove the solvent to obtain mixed powder;
(2) Grinding and crushing the obtained powder, then filling the powder into a supercritical carbon dioxide reaction device, vacuumizing the supercritical carbon dioxide reaction device, and then introducing carbon dioxide gas, wherein the pressure is controlled to be 7 to 25MPa, the temperature is controlled to be 33 to 60 ℃, and the temperature is kept for 6 to 24 hours;
and releasing the gas in the reaction device to obtain the anode material or the cathode material coated with the 1-50 nm thick lithium carbonate coating.
2. The high specific energy aqueous lithium ion battery of claim 1, wherein: the lithium salt is at least one of lithium perchlorate, lithium nitrate, lithium sulfate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (pentafluoroethylsulfonyl) imide.
3. The high specific energy aqueous lithium ion battery according to claim 1 or 2, wherein: the mass ratio of the hydrogen evolution inhibitor to the lithium salt is 2~7:8~3.
4. The high specific energy aqueous lithium ion battery of claim 3, wherein: the content of water in the aqueous electrolyte is 5 to 30% of the sum of the masses of the lithium salt and the hydrogen evolution inhibitor.
5. The high specific energy aqueous lithium ion battery of claim 1, wherein: the positive current collector is selected from titanium foil, stainless steel foil or carbon paper, and the negative current collector is selected from aluminum foil or stainless steel foil.
6. The high specific energy aqueous lithium ion battery of claim 1, wherein: the diaphragm is one selected from glass fiber, polypropylene and cellulose.
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