CN113193174A - Interface pretreatment liquid for silica prelithiation negative electrode and preparation method and application thereof - Google Patents
Interface pretreatment liquid for silica prelithiation negative electrode and preparation method and application thereof Download PDFInfo
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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Abstract
The invention relates to an interface pretreatment liquid for a silica prelithiation cathode, a preparation method and application thereof, wherein the interface pretreatment liquid comprises 0.1-10% of solute and 90-99.9% of solvent; the solvent is selected from one or more of N-methyl pyrrolidone, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, ethyl formate, methyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1, 3-dioxolane, dimeric ethylene glycol dimethyl ether and dimethyl sulfoxide; the solute is selected from one or more of lithium polysulfide, aluminum iodide, aluminum bromide, lithium nitrate and copper nitride. The solvent can fully infiltrate the inner pores of the lithium-rich negative plate and the surface of the negative active material, and the solute can react with the negative material, so that the stability of the SEI film is improved, and the first charge-discharge efficiency and the long-term cycle performance of the battery are synergistically improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an interface pretreatment solution for a silica prelithiation cathode, and a preparation method and application thereof.
Background
In recent years, in order to meet the requirements of rapid development of new energy automobiles, smart power grids, distributed energy storage and the like, development of lithium ion batteries with high energy density, high safety and long cycle life becomes a research hotspot in the current energy storage field. The improvement of the energy density of the battery mainly depends on the development of key electrode materials, such as the continuous improvement of the capacities of positive and negative electrode materials. The conventional lithium ion battery cathode is close to the limit, and in order to meet the energy requirement of a new generation and improve the energy density of the battery, the development of a novel lithium battery cathode technology is urgent.
The lithium storage theoretical capacity of silicon is more than 10 times of the capacity of graphite, and can reach 4200mAh/g, and the safety performance of silicon is superior to that of a graphite cathode material, because the voltage platform of silicon is higher than that of graphite, lithium is not easy to precipitate on the surface of silicon in the charging and discharging process, and the safety of the battery is improved. Meanwhile, as one of the most abundant elements in the nature, the silicon has wide sources and low manufacturing cost. The high-nickel ternary-matched silicon-carbon system is focused by more and more cell manufacturers and material researchers due to the unique advantages of the high-nickel ternary-matched silicon-carbon system in energy density, and the energy density of a single cell is expected to be improved to be more than 300 Wh/kg.
Although the high-nickel ternary collocation silicon-carbon system has the energy density advantage incomparable to other positive and negative electrode systems, the rapid capacity attenuation of the silicon material in the circulating process seriously hinders the practical process. This is because, after lithium intercalation during charging, the volume of silicon atoms expands 3 times or more, thereby destroying the original solid electrolyte interface film (SEI) on the surface and rapidly lowering the capacity and cycle performance of the battery.
Currently, commercial silicon substratesThe cathode material is mainly silicon oxide (SiO)x) Compounding with graphite, SiO during first chargingxWith Li+React to form Li2O、Li4SiO4For example, lithium from the positive electrode is irreversibly consumed, resulting in low first charge-discharge efficiency and large irreversible capacity loss. The lithium supplement material is used for carrying out pre-lithiation on the silicon-based negative electrode, so that the irreversible lithium loss is counteracted, the first charge-discharge efficiency and the reversible specific capacity of the battery are improved, and a material solution is provided for the industrial application of the high-specific-energy battery.
After lithium is supplemented, lithium intercalation reaction can be immediately carried out on the negative plate after electrolyte is injected to generate SEI, lithium in a simple substance state is used as a lithium supplementing lithium source and can provide lithium ions and electrons at the same time, the electrons can continuously carry out side reaction with a solvent to generate substances such as alkyl lithium carbonate and alkyl lithium with unstable thermodynamics and kinetics, the SEI is not stable enough, and the first charge-discharge efficiency and the cycle life of the lithium ion secondary battery are influenced to a certain extent.
Relevant reports have been made on how to improve the stability of the SEI of the pre-lithiated negative electrode, for example, patent CN110875499 provides a method for supplementing lithium for a battery, in which a layer of lithium metal is disposed on the surface of a negative electrode sheet to obtain a lithium-rich negative electrode sheet; assembling the lithium-rich cathode plate, the isolating membrane and the anode plate into a lithium supplement core; soaking the lithium supplement core in an organic solvent for a period of time, wherein the organic solvent comprises a negative electrode film forming component; and (4) placing the soaked lithium supplement battery core in a battery packaging shell, injecting electrolyte and packaging to obtain the lithium supplement battery. Therefore, the inner pores of the lithium-rich negative plate and the surface of the negative active material are fully infiltrated by the negative film forming component in advance, and the negative film forming component can uniformly wrap the negative active material so as to form a film preferentially.
Patent CN 103035952 provides a method for injecting electrolyte into lithium ion battery, in which a battery cell to be injected containing a lithium-rich negative plate and the electrolyte are cooled and injected, and after the completion of pre-lithiation, the temperature is raised to perform formation. The method can effectively control the lithium intercalation speed in the pre-lithiation process, and improve the structural stability of SEI (solid electrolyte interphase), so that the first charge-discharge efficiency and capacity are improved, and the cycle performance of the battery is improved. However, the energy consumption is increased by the cooling treatment, and the low temperature of-50 ℃ is required to obtain obvious effect, so that the large-scale application of the composite material is limited.
In summary, the methods adopted at present have certain problems in operability, universality and practical effects, cannot well improve the stability of the SEI of the pre-lithiation negative electrode, and have limitations in improving the first charge-discharge efficiency and cycle life of the lithium ion secondary battery.
Disclosure of Invention
Aiming at the problems, the invention provides the interface pretreatment solution for the silica pre-lithiation negative electrode, which can obviously improve the first charge-discharge efficiency and the cycle life of the lithium ion secondary battery.
The technical scheme is as follows:
an interface pretreatment liquid for a silica-prelithiation cathode comprises 0.1-10% of solute and 90-99.9% of solvent by mass percent;
the solvent is selected from one or more mixed solvents of N-methyl pyrrolidone, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, ethyl formate, methyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1, 3-dioxolane, dimeric ethylene glycol dimethyl ether and dimethyl sulfoxide;
the solute is selected from one or more of lithium polysulfide, aluminum iodide, aluminum bromide, lithium nitrate and copper nitride.
In one embodiment, the interface pretreatment solution for the silicon-oxygen pre-lithiation negative electrode comprises 0.5-8% of a solute and 92-99.5% of a solvent by mass percent.
In one embodiment, the interface pretreatment solution for the silicon-oxygen pre-lithiation negative electrode comprises 1-5% of solute and 95-99% of solvent by mass percent.
In one embodiment, the solvent is selected from a mixed solvent of one or more of ethylene glycol dimethyl ether, 1, 3-dioxolane, dimeric ethylene glycol dimethyl ether and dimethylene sulfide.
In one embodiment, the lithium polysulfide is prepared from (6-10): 1 and lithium sulfide.
The invention also provides a preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode, which comprises the following steps:
controlling the water content to be less than 1ppm and the oxygen content to be less than 1ppm in an inert gas atmosphere, and mixing the solute and the solvent.
The invention also provides an interface pretreatment method of the silicon-oxygen pre-lithiation cathode, which comprises the following steps:
the prelithiation pole piece is soaked in the interface pretreatment solution for the silica prelithiation negative electrode as described in any of the above embodiments.
In one embodiment, the soaking time is 1-25 min.
In one embodiment, the soaking time is 2min to 15 min.
In one embodiment, after the soaking treatment, the method further comprises a step of drying the pre-lithiation pole piece.
In one embodiment, the soaking treatment and the drying treatment are carried out under the conditions of inert gas atmosphere, oxygen content of less than 1ppm and water content of less than 1 ppm.
The invention also provides a method for supplementing lithium for the battery, which comprises the following steps:
coating positive slurry containing a positive active material on the surface of a positive current collector, and drying to obtain a positive plate with a positive diaphragm arranged on the surface of the positive current collector;
coating negative electrode slurry containing a negative electrode active substance on the surface of a negative electrode current collector, drying to obtain an initial negative electrode plate with a negative electrode diaphragm arranged on the surface of the negative electrode current collector, and then continuously arranging a layer of lithium metal on the surface of the negative electrode diaphragm to obtain a lithium-supplementing negative electrode plate;
soaking the lithium-supplementing negative plate in interface pretreatment liquid for silica pre-lithiation of the negative electrode for 1-25 min, and drying to obtain a negative electrode material;
assembling a negative electrode material, a diaphragm and a positive plate into a lithium supplement cell;
and (4) placing the lithium supplement cell in a cell packaging shell, injecting electrolyte and packaging to obtain the lithium supplement cell.
Compared with the prior art, the invention has the following beneficial effects:
the interface pretreatment liquid for the silicon-oxygen pre-lithiation cathode comprises 0.1-10% of specific solute and 90-99.9% of solvent. The specific solvent has good chemical stability, strong solubility and moderate surface tension, and the reagents are used as the solvent of the interface pretreatment solution, so that the internal pores of the lithium-rich negative plate and the surface of the negative active material can be fully infiltrated; specific solutes that can react with the anode material, such as lithium polysulfide (Li)2Sx) Reacting with metallic lithium (Li) to form lithium sulfide (Li)2S) and lithium disulfide (Li)2S2) Lithium nitrate (LiNO)3) Reduced to lithium nitrite (LiNO) by metallic lithium (Li)2) Decomposed to form lithium-containing ion conductor (Li) during charging and discharging3N and LiNxOy) SEI of (1), aluminum iodide (AlI)3) Reacting with metallic lithium (Li) to produce lithium iodide (LiI) and aluminum bromide (AlBr)3) Reacting with metallic lithium (Li) to produce lithium bromide (LiBr), copper nitride (CuN)3) Reacts with metallic lithium (Li) to form lithium nitride (Li)3N), the products have good mechanical properties and electrochemical stability, and can effectively inhibit the growth of lithium dendrites and the occurrence of side reactions, so that an SEI film formed on the surface of the pre-lithiated negative electrode is more stable. The solvent and the solute are matched with each other, so that the components and the structure of the silicon-oxygen pre-lithiation cathode SEI film can be optimized, the occurrence of side reactions is reduced, the uniformity of SEI and lithium deposition is improved, and the first charge-discharge efficiency and the long-term cycle performance of the battery are improved.
In addition, the interface pretreatment liquid disclosed by the invention is simple in preparation method and use method, only the negative electrode plate needs to be soaked in the interface pretreatment liquid in the application process, the soaking time is short, the action effect is good, the production efficiency is high, the time and the energy consumption can be saved, and the production cost is reduced.
Tests prove that the interface pretreatment liquid for the silicon-oxygen pre-lithiation cathode prepared by the invention can still keep more than 90% of capacity after being circulated for 200 times, has good cycle performance, meets the product requirements, is simple to operate, is suitable for industrial production, and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
The method adopted at present has certain problems in the aspects of operability, universality and actual effect, can not well improve the stability of the SEI of the pre-lithiation cathode, and has limitations in the aspects of improving the first charge-discharge efficiency and prolonging the cycle life of the lithium ion secondary battery.
The interface pretreatment solution for the silica pre-lithiation cathode provided by the invention can obviously improve the first charge-discharge efficiency and the cycle life of a lithium ion secondary battery, is simple to operate and has high treatment efficiency.
The technical scheme is as follows:
an interface pretreatment liquid for a silica-prelithiation cathode comprises 0.1-10% of solute and 90-99.9% of solvent by mass percent;
the solvent is selected from one or more mixed solvents of N-methyl pyrrolidone, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, ethyl formate, methyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1, 3-dioxolane, dimeric ethylene glycol dimethyl ether and dimethyl sulfoxide;
the solute is selected from one or more of lithium polysulfide, aluminum iodide, aluminum bromide, lithium nitrate and copper nitride.
The solvent has good chemical stability, strong solubility and moderate surface tension, and the adoption of the reagents as the solvent of the interface pretreatment solution can fully infiltrate the internal pores of the lithium-rich negative plate and the surface of the negative active material. The solute can react with the negative electrode material, so that an SEI film formed on the surface of the pre-lithiated negative electrode is more stable, the side reaction between the metal lithium and the electrolyte is slowed down or relieved, and the first charge-discharge efficiency and the long-term cycle performance of the battery are synergistically improved.
In one preferred embodiment, the solvent is selected from one or more of glyme, 1, 3-dioxolane, dimer glyme, and dimethylsulfide. Such a solvent is more advantageous to improve the stability of the SEI film.
In one preferred embodiment, the solute is selected from one or more of lithium polysulfide, aluminum iodide, and aluminum bromide. Such a solute is more advantageous to improve the stability of the SEI film.
In one embodiment, the lithium polysulfide is prepared from (6-10): 1 and lithium sulfide.
In one preferable embodiment, the interface pretreatment solution for the silicon-oxygen pre-lithiation negative electrode comprises, by mass, 0.5% to 8% of a solute and 92% to 99.5% of a solvent.
Further, the interface pretreatment liquid for the silicon-oxygen pre-lithiation negative electrode comprises, by mass, 1% -5% of a solute and 95% -99% of a solvent.
The invention also provides a preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode, which comprises the following steps:
controlling the water content to be less than 1ppm and the oxygen content to be less than 1ppm in an inert gas atmosphere, and mixing the solute and the solvent.
The inert gas according to the present invention includes helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radioactive radon (Rn), and they are colorless and odorless monatomic gases at normal temperature and pressure, and are difficult to chemically react.
The invention also provides an interface pretreatment method of the silicon-oxygen pre-lithiation cathode, which comprises the following steps:
the prelithiation pole piece is soaked in the interface pretreatment solution for the silica prelithiation negative electrode as described in any of the above embodiments.
The application method is simple, only the negative pole piece needs to be soaked in the interface pretreatment liquid in the application process, the soaking time is short, the action effect is good, the production efficiency is high, the time and the energy consumption can be saved, and the production cost is reduced.
In one embodiment, the soaking time is 1-25 min.
In one embodiment, the soaking time is 2min to 15 min.
In one embodiment, after the soaking treatment, the method further comprises a step of drying the pre-lithiation pole piece. Preferably, the drying time is 1 to 5 hours.
In one embodiment, the soaking treatment and the drying treatment are carried out under the conditions of inert gas atmosphere, oxygen content of less than 1ppm and water content of less than 1 ppm. Preferably, it is carried out in an argon atmosphere glove box.
The invention also provides a method for supplementing lithium for the battery, which comprises the following steps:
coating positive slurry containing a positive active material on the surface of a positive current collector, and drying to obtain a positive plate with a positive diaphragm arranged on the surface of the positive current collector;
coating negative electrode slurry containing a negative electrode active substance on the surface of a negative electrode current collector, drying to obtain an initial negative electrode plate with a negative electrode diaphragm arranged on the surface of the negative electrode current collector, and then continuously arranging a layer of lithium metal on the surface of the negative electrode diaphragm to obtain a lithium-supplementing negative electrode plate;
soaking the lithium-supplementing negative plate in interface pretreatment liquid for silica pre-lithiation of the negative electrode for 1-25 min, and drying to obtain a negative electrode material;
assembling a negative electrode material, a diaphragm and a positive plate into a lithium supplement cell;
and (4) placing the lithium supplement cell in a cell packaging shell, injecting electrolyte and packaging to obtain the lithium supplement cell.
Preferably, the lithium-supplementing negative plate is soaked in the interface pretreatment solution for silica pre-lithiation of the negative electrode for 2min to 15min and dried to prepare the negative electrode material. More preferably, the lithium-supplementing negative plate is soaked in the interface pretreatment solution for silica pre-lithiation of the negative electrode for 5min to 10min and dried to prepare the negative electrode material.
The present invention will be further described with reference to specific examples.
Example 1
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
1% of lithium polysulfide and 99% of ethylene glycol dimethyl ether; the lithium polysulfide is prepared by sulfur and lithium sulfide according to the molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 1 wt% is prepared.
(3) Preparing a lithium ion battery:
the method comprises the following steps: preparation of Positive plate
LiNi as positive electrode active material0.8Co0.1Mn0.1O2Mixing the conductive carbon black, the carbon nano tube and the polyvinylidene fluoride binder according to the mass ratio of 97:0.5:0.5:2, adding a solvent N-methyl pyrrolidone, fully stirring and uniformly mixing to obtain positive electrode slurry, and coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, wherein the coating mass of the positive electrode slurry is 1.524g/76.2cm2(single side, based on the mass of the solid component without solvent), drying and cold pressing to obtain the positive plate.
Step two: preparation of lithium-supplementing negative plate
Mixing a negative electrode active substance of silicon monoxide, graphite, conductive carbon black, a carbon nano tube, a sodium carboxymethyl cellulose binder and styrene butadiene rubber according to a mass ratio of 14.4:81.4:0.04:1.20:2.50, adding deionized water as a solvent, fully stirring and uniformly mixing to obtain negative electrode slurry, and then coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil, wherein the coating mass of the negative electrode slurry is 0.709g/80.6cm2(single side, calculated by the mass of solid components not containing solvent), drying and cold pressing to obtain an initial negative plate, and coating lithium powder (theoretical gram capacity of 3760mAh/g) on the surface of the initial negative plate to obtain a lithium-supplement negative plate, wherein the mass of the lithium powder is 25.08mg//80.6cm2And (6) cutting.
Step three: the interface pretreatment is carried out on the lithium-supplementing negative plate
In an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, the cut lithium-supplement negative plate is soaked in the interface pretreatment liquid of the embodiment for 5min, and then dried at normal temperature for 2h in an argon atmosphere to obtain the negative electrode material.
Step four: preparation of the electrolyte
In an argon atmosphere glove box with water content less than 1ppm and oxygen content less than 1ppm, mixing ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and fluoroethylene carbonate according to mass percent of 20%, 30%, 40% and 10% to obtain a mixed organic solvent, dissolving dried lithium hexafluorophosphate in the mixed organic solvent, wherein the concentration of the lithium hexafluorophosphate is 1mol/L, adding vinylene carbonate accounting for 1% of the electrolyte by mass as an additive, and uniformly stirring to obtain the electrolyte.
Step five: preparation of the separator
A polyethylene porous membrane with both sides coated with alumina ceramic was used as a separator.
Step six: preparation of a Battery
And stacking the positive plate, the diaphragm and the negative electrode material in sequence to enable the diaphragm to be positioned between the positive electrode and the negative electrode to play a role of isolation to obtain a lithium supplement cell, placing the lithium supplement cell in a battery packaging shell, injecting the prepared electrolyte and packaging to obtain the lithium ion battery.
Example 2
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
2% of lithium polysulfide and 98% of ethylene glycol dimethyl ether; the lithium polysulfide is prepared from sulfur and lithium sulfide according to a molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 3
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
3% of lithium polysulfide and 97% of ethylene glycol dimethyl ether; the lithium polysulfide is prepared from sulfur and lithium sulfide according to a molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 3 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 4
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
1% of lithium nitrate and 99% of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether and lithium nitrate are sequentially added into an aluminum plastic bottle, the mixture is stirred for 1 hour until the lithium nitrate is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 1 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 5
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
2 percent of lithium nitrate and 98 percent of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether and lithium nitrate are sequentially added into an aluminum plastic bottle, the mixture is stirred for 1 hour until the lithium nitrate is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 6
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
3 percent of lithium nitrate and 97 percent of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether and lithium nitrate are sequentially added into an aluminum plastic bottle, the mixture is stirred for 1 hour until the lithium nitrate is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 3 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 7
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
2% of aluminum bromide and 98% of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether and aluminum bromide are sequentially added into an aluminum-plastic bottle, the mixture is stirred for 1 hour until the aluminum bromide is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 8
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
2% of aluminum iodide and 98% of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether and aluminum iodide are sequentially added into an aluminum-plastic bottle, stirred for 1h until the aluminum iodide is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 9
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
copper nitride 2% and ethylene glycol dimethyl ether 98%.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box containing less than 1ppm of water and less than 1ppm of oxygen, ethylene glycol dimethyl ether and copper nitride are sequentially added into an aluminum-plastic bottle, stirred for 1 hour until the copper nitride is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 10
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
2% of lithium polysulfide and 98% of 1, 3-dioxolane; the lithium polysulfide is prepared from sulfur and lithium sulfide according to a molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content less than 1ppm and the oxygen content less than 1ppm, 98% of 1, 3-dioxolane is added into an aluminum-plastic bottle, then sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 11
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
lithium polysulfide 2% and dimer ethylene glycol dimethyl ether 98%; the lithium polysulfide is prepared by sulfur and lithium sulfide according to a molar ratio.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, adding the dimeric ethylene glycol dimethyl ether into an aluminum-plastic bottle, adding sulfur and lithium sulfide into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring for 1h until the sulfur and the lithium sulfide are completely dissolved, and preparing an interface pretreatment solution with the solute being lithium polysulfide and the solute mass fraction being 2 wt%.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 12
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
lithium polysulfide 2% and dimethylsulfide 98%; the lithium polysulfide is prepared from sulfur and lithium sulfide according to a molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode in the embodiment comprises the following steps:
adding dimethyl sulfoxide into an aluminum-plastic bottle in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, adding sulfur and lithium sulfide into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring for 1h until the sulfur and the lithium sulfide are completely dissolved, and preparing an interface pretreatment solution with the solute being lithium polysulfide and the solute mass fraction being 2 wt%.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 13
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
lithium polysulfide 0.5% and ethylene glycol dimethyl ether 99.5%; the lithium polysulfide is prepared by sulfur and lithium sulfide according to the molar ratio of 8: 1.
(2) The preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode in the comparative example comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 8:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 0.5 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Example 14
The embodiment provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode, and a preparation method and application thereof.
(1) In this embodiment, the interface pretreatment solution for the silicon-oxygen prelithiation negative electrode includes, by mass:
8% of lithium polysulfide and 92% of ethylene glycol dimethyl ether; the lithium polysulfide is prepared by sulfur and lithium sulfide according to the molar ratio of 8: 1.
(2) The preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode in the comparative example comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 8:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 8 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Comparative example 1
The lithium ion battery of this comparative example was completely the same as example 1 except that no interface pretreatment was performed on the lithium-complementary negative electrode sheet.
Comparative example 2
The interface pretreatment solution for the silica pre-lithiation cathode provided by the comparative example is ethylene glycol dimethyl ether, and the preparation process of the lithium ion battery is the same as that of example 1.
Comparative example 3
The interface pretreatment solution for the silica pre-lithiation cathode provided by the comparative example is 1, 3-dioxolane, and the preparation process of the lithium ion battery is the same as that of example 1.
Comparative example 4
The interface pretreatment solution for the silica pre-lithiation cathode provided by the comparative example is diethylene glycol dimethyl ether, and the preparation process of the lithium ion battery is the same as that in example 1.
Comparative example 5
The interface pretreatment solution for the silicon-oxygen pre-lithiated negative electrode provided by the comparative example is dimethyl sulfide, and the preparation process of the lithium ion battery is the same as that in example 1.
Comparative example 6
The comparative example provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode and a preparation method and application thereof.
(1) The interface pretreatment liquid for the silicon-oxygen pre-lithiation negative electrode in the comparative example comprises the following components in percentage by mass:
lithium acetate 2% and ethylene glycol dimethyl ether 98%.
(2) The preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode in the comparative example comprises the following steps:
in an argon atmosphere glove box with the water content less than 1ppm and the oxygen content less than 1ppm, ethylene glycol dimethyl ether and lithium acetate are sequentially added into an aluminum-plastic bottle, stirred for 1h until the lithium acetate is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Comparative example 7
The comparative example provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode and a preparation method and application thereof.
(1) The interface pretreatment liquid for the silicon-oxygen pre-lithiation negative electrode in the comparative example comprises the following components in percentage by mass:
2% of lithium hydroxide and 98% of ethylene glycol dimethyl ether.
(2) The preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode in the comparative example comprises the following steps:
in an argon atmosphere glove box with the water content less than 1ppm and the oxygen content less than 1ppm, ethylene glycol dimethyl ether and lithium hydroxide are sequentially added into an aluminum-plastic bottle, stirred for 1 hour until the lithium hydroxide is completely dissolved, and interface pretreatment liquid with the solute mass fraction of 2 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
Comparative example 8
The comparative example provides an interface pretreatment solution for a silicon-oxygen pre-lithiation negative electrode and a preparation method and application thereof.
(1) The interface pretreatment liquid for the silicon-oxygen pre-lithiation negative electrode in the comparative example comprises the following components in percentage by mass:
20% of lithium polysulfide and 80% of ethylene glycol dimethyl ether; the lithium polysulfide is prepared by sulfur and lithium sulfide according to the molar ratio of 7: 1.
(2) The preparation method of the interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode in the comparative example comprises the following steps:
in an argon atmosphere glove box with the water content of less than 1ppm and the oxygen content of less than 1ppm, ethylene glycol dimethyl ether is added into an aluminum-plastic bottle, sulfur and lithium sulfide are added into the aluminum-plastic bottle according to the molar ratio of 7:1, stirring is carried out for 1h until the sulfur and the lithium sulfide are completely dissolved, and interface pretreatment liquid with the solute being lithium polysulfide and the solute mass fraction being 20 wt% is prepared.
(3) The procedure for the preparation of the lithium ion battery was the same as in example 1.
1. The compositions of the interfacial pretreatment liquids in examples 1 to 13 and comparative examples 2 to 8 are shown in table 1.
TABLE 1
2. Testing
At 25 ℃, the battery is charged to 3.9V at a constant current of 0.02C, then charged to 4.25V at a constant current of 0.2C, and after standing for 5min, the battery is discharged to 2.5V at a constant current of 0.2C, which is a first charge-discharge process, and then is subjected to multiple charge-discharge cycles at a charge/discharge rate of 0.33C/0.33C, and the first charge-discharge efficiency and the capacity retention rate of 200 cycles of the lithium ion batteries of examples 1 to 14 and comparative examples 1 to 8 are respectively tested, and the first charge-discharge efficiency and cycle performance test results of the lithium ion batteries of the examples and comparative examples are shown in Table 2.
TABLE 2
The first charge-discharge efficiency and the cycle performance of the lithium ion batteries in the embodiments 1 to 14 are obviously superior to those of the comparative examples, and it can be known that the interface filming of the pre-lithiation negative electrode can be obviously improved by performing interface pretreatment on the lithium-supplement negative electrode sheet, so that the first charge-discharge efficiency and the cycle performance are effectively improved.
In comparative example 1, since interface pretreatment was not performed on the lithium-supplement negative electrode sheet, the SEI film formed on the surface of the prelithiation negative electrode was not stable enough, and the side reaction between lithium metal lithium and the electrolyte was aggravated, thereby affecting the first charge-discharge efficiency and cycle life of the battery.
In comparative examples 2-5, since no solute is added, the solvent itself cannot react with the lithium metal, the components and structure of the negative electrode SEI film are not improved, and substances such as alkyl lithium carbonate and alkyl lithium with unstable thermodynamics and kinetics are generated in the subsequent lithium intercalation process, so that the SEI is not stable enough, and the first charge-discharge efficiency and the cycle life of the battery are further influenced.
In comparative examples 6 to 7, the solute cannot react with metallic lithium, so that interface film formation of the pre-lithiated negative electrode cannot be improved, the lithium-insertion reaction and SEI generation can be immediately performed on the lithium-supplement negative electrode piece after the electrolyte is injected, lithium in a simple substance state is used as a lithium-supplement lithium source, lithium ions and electrons can be simultaneously provided, the electrons can continuously perform side reaction with the solvent, and the first charge-discharge efficiency and the cycle life of the lithium ion secondary battery are influenced to a certain extent. Therefore, a suitable solute must be added to react with the lithium metal to form a thermodynamically and kinetically stable interfacial layer.
In comparative example 8, the interface film formation of the prelithiated negative electrode was too thick due to too high mass percent of solute, increasing the battery impedance, and lithium was easily separated during cycling to cause cycle water breakthrough, affecting cycle life.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. An interface pretreatment liquid for a silica-prelithiation cathode is characterized by comprising 0.1-10% of solute and 90-99.9% of solvent by mass percent;
the solvent is selected from one or more mixed solvents of N-methyl pyrrolidone, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, ethyl formate, methyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1, 3-dioxolane, dimeric ethylene glycol dimethyl ether and dimethyl sulfoxide;
the solute is selected from one or more of lithium polysulfide, aluminum iodide, aluminum bromide, lithium nitrate and copper nitride.
2. The interfacial pretreatment liquid for the silicon-oxygen prelithiation negative electrode according to claim 1, comprising 0.5-8% of solute and 92-99.5% of solvent by mass%.
3. The interface pretreatment liquid for the silicon-oxygen prelithiation negative electrode according to claim 2, comprising 1-5% of solute and 95-99% of solvent by mass percent.
4. The interfacial pretreatment liquid for a silicon-oxygen prelithiation negative electrode according to any one of claims 1 to 3, wherein the solvent is a mixed solvent of one or more selected from the group consisting of ethylene glycol dimethyl ether, 1, 3-dioxolane, dimer ethylene glycol dimethyl ether, and dimethyl sulfide.
5. The interfacial pretreatment liquid for the silicon-oxygen prelithiation negative electrode according to claim 4, wherein the lithium polysulfide is prepared from the following components in a molar ratio of (6-10): 1 and lithium sulfide.
6. The method for preparing an interfacial pretreatment liquid for a silicon-oxygen prelithiated anode of any one of claims 1 to 5, comprising the steps of:
controlling the water content to be less than 1ppm and the oxygen content to be less than 1ppm in an inert gas atmosphere, and mixing the solute and the solvent.
7. An interface pretreatment method of a silicon-oxygen pre-lithiated negative electrode is characterized by comprising the following steps of:
soaking the pre-lithiated pole piece in the interface pretreatment solution for the silicon-oxygen pre-lithiated negative electrode in any one of claims 1 to 5.
8. The interface pretreatment method of the silicon-oxygen prelithiation negative electrode according to claim 7, wherein the soaking time is 1-25 min.
9. The interface pretreatment method of the silicon-oxygen pre-lithiated negative electrode according to claim 7 or 8, further comprising a step of drying the pre-lithiated pole piece after the soaking treatment.
10. The method of interfacial pretreatment of silicon-oxygen prelithiation negative electrodes of claim 9, wherein the soaking and drying are performed under inert gas atmosphere with oxygen content <1ppm and water content <1 ppm.
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