CN116995292A - Method for inhibiting lithium ion battery from precipitating lithium - Google Patents
Method for inhibiting lithium ion battery from precipitating lithium Download PDFInfo
- Publication number
- CN116995292A CN116995292A CN202210446340.1A CN202210446340A CN116995292A CN 116995292 A CN116995292 A CN 116995292A CN 202210446340 A CN202210446340 A CN 202210446340A CN 116995292 A CN116995292 A CN 116995292A
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- China
- Prior art keywords
- lithium
- ion battery
- lithium ion
- temperature
- precipitation
- Prior art date
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- Pending
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 120
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 118
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 20
- 230000001376 precipitating effect Effects 0.000 title description 3
- 210000001787 dendrite Anatomy 0.000 claims abstract description 56
- 238000001556 precipitation Methods 0.000 claims abstract description 53
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- 238000012423 maintenance Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 31
- 239000011889 copper foil Substances 0.000 description 31
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
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- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 description 1
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- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/443—Methods for charging or discharging in response to temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to a method for inhibiting lithium precipitation of a lithium ion battery, which comprises the following steps: a) Heating the lithium ion battery to a temperature of 40 ℃ to 80 ℃; and b) aging the lithium ion battery at the temperature of step a) for 10 hours to 100 hours. The method disclosed by the application can obviously reduce the precipitation and/or growth of lithium dendrites in the lithium ion battery, thereby improving the discharge capacity of the lithium ion battery and improving the safety of the lithium ion battery.
Description
Technical Field
The application relates to a method for inhibiting lithium precipitation of a lithium ion battery, comprising heating the lithium ion battery to a temperature of 40-80 ℃ and subsequently aging the lithium ion battery at this temperature for 10-100 hours.
Background
The lithium ion battery becomes the most popular energy storage system due to the characteristics of low cost, long service life, good safety and the like, and is widely applied to the fields of pure electric vehicles, hybrid electric vehicles, smart grids and the like. However, lithium ion batteries present a risk of lithium precipitation during charging. Particularly, when high-current rapid charge or low-temperature charge is performed, the speed of lithium ion intercalation into the negative electrode is smaller than the speed of lithium ion conduction to the negative electrode active material, so that metallic lithium is precipitated on the surface of the negative electrode plate. Dendritic lithium metal crystals, abbreviated as lithium dendrites, are typically formed during lithium metal precipitation and deposition. Lithium dendrites are prone to various side reactions with the electrolyte, producing large amounts of gas and heat. Meanwhile, lithium dendrites may pierce through the separator film, resulting in a short circuit or even a combustion explosion of the lithium battery. Therefore, there is a need to widely inhibit lithium dendrite growth and improve battery safety.
In the prior art, the separator is subjected to electrical modification or mechanical modification to improve the performance of the separator, or an additive is added into the electrolyte to avoid precipitation of lithium as much as possible. However, precipitation of lithium dendrites is almost an unavoidable phenomenon during the life cycle of commercial lithium ion batteries. Accordingly, there is a need in the art for a method that can inhibit precipitation and/or growth of lithium dendrites during the entire life cycle of a lithium ion battery.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to provide a method for suppressing lithium precipitation in a lithium ion battery, which can effectively suppress precipitation and/or growth of lithium dendrites over the entire life cycle of the lithium ion battery, thereby solving the technical problems that the lithium ion battery capacity is reduced and the safety risk is increased due to unavoidable growth of lithium dendrites in the prior art.
In order to achieve the above object, a first aspect of the present application provides a method for inhibiting lithium precipitation of a lithium ion battery, comprising the steps of:
a) Heating the lithium ion battery to a temperature of 40 ℃ to 80 ℃; and
b) Aging the lithium ion battery at the temperature of step a) for 10 hours to 100 hours.
By heating the lithium ion battery to a specific temperature that is elevated compared to room temperature and aging at that temperature for a period of time, a portion of the lithium dendrites thermally "melt" and simultaneously passivate the surface of the formed lithium dendrites, effectively reducing lithium dendrite reactivity and inhibiting continued growth thereof.
Reactions that may occur in this process include, but are not limited to, the following reaction equations:
C 3 H 4 O 3 (EC)+2Li→Li 2 CO 3 +C 2 H 4 ；
C 4 H 8 O 3 (EMC)+2Li→Li 2 CO 3 +C 3 H 8 。
in any embodiment, the method comprises heating the lithium ion battery to a temperature of 45 ℃ to 70 ℃, optionally to a temperature of 55 ℃ to 65 ℃ in step a). By selecting a specific temperature range for aging, a better passivation effect can be achieved, so that the technical effect of inhibiting lithium precipitation is further improved.
In any embodiment, the method comprises in step b) aging the lithium ion battery at the temperature of step a) for 40 hours to 70 hours. By specific selection of the aging time, the effect of suppressing the growth of lithium dendrites can be further optimized. In some embodiments, the aging in step b) is accomplished by standing at the above temperature.
In any embodiment, in said step b), the temperature of aging is kept constant over time or varies in a gradient form over time. By means of an adjustable temperature gradient, the effect of suppressing lithium precipitation can be more effectively adjusted.
In any embodiment, the method further comprises the steps of: before heating, the lithium ion battery is disassembled and reassembled, and the discharge capacity is measured to judge the lithium precipitation amount of the negative pole piece of the lithium ion battery. In any embodiment, the method further comprises the steps of: and adjusting the heating temperature and aging time according to the lithium precipitation amount of the negative electrode plate of the lithium ion battery. By setting the aging procedure for a specific lithium amount of the lithium battery, it is possible to improve the efficiency of suppressing lithium precipitation, reduce energy consumption, and reduce the risk of thermal runaway.
In any embodiment, the lithium ion battery is a battery that is returned to service after use. In some embodiments, the lithium precipitation is the precipitation and growth of lithium dendrites. After the aging treatment, the surface of the lithium dendrites is passivated.
In any embodiment, the method further comprises charging the lithium ion battery and standing until its internal resistance value remains in a steady state prior to heating.
In any embodiment, the lithium ion battery is not charged or discharged in steps a) and b) of the method. In any embodiment, the steps a) and b) are performed at atmospheric pressure.
Drawings
In order to more clearly illustrate the technical solution of the present application, the following will briefly describe the drawings that are required to be used in the embodiments of the present application. It is apparent that the drawings described below are only some embodiments of the present application and that other drawings may be obtained from the drawings without inventive work for those of ordinary skill in the art.
Fig. 1 is a side view of a lithium ion battery of a tailored, directional lithium-ion battery used in an embodiment of the application for detecting a short circuit resistance, wherein an internal resistance meter connecting a negative electrode tab with a copper foil electrode is not shown.
Fig. 2 is a graph showing a change in resistance value measured by the internal resistance meter with an increase in temperature from 25 to 60 c and with standing for various times in the embodiment of the present application.
Description of the reference numerals
1 copper foil electrode
2 negative pole piece
3 positive pole piece
4 isolating film
5 insulating part
6 insulating glue
Detailed Description
For simplicity, the present application specifically discloses some numerical ranges. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
After a lithium ion battery undergoes a plurality of charge and discharge cycles during use, a phenomenon of lithium precipitation is inevitably generated. The main reason is that the speed of lithium ion intercalation into the negative electrode is smaller than the speed of lithium ion migration into the negative electrode active material, so that the rest of lithium ions incapable of intercalating into the negative electrode are deposited and separated out on the surface of the negative electrode plate in the form of metallic lithium. The metallic lithium is usually present in the form of dendrites, called lithium dendrites, when precipitated. Lithium dendrites have a very high specific surface area, and thus are liable to undergo various side reactions with an electrolyte, increase gas yield and reduce battery capacity. When lithium dendrites grow excessively, they pierce the separator film, causing a short circuit or even a combustion explosion of the battery. Some methods for inhibiting the growth of lithium dendrites have been developed in the prior art, mainly comprising modification of electrode sheets and separator films and addition of specific additives to the electrolyte. These methods are costly or complex to operate and cannot specifically inhibit the lithium ion battery from precipitating lithium over the entire life cycle.
The present inventors have found that precipitation and/or growth of lithium dendrites in a lithium ion battery can be effectively suppressed or even reduced by aging the lithium ion battery at a temperature in a specific range higher than room temperature for a specific period of time.
Specifically, the first aspect of the present application provides a method for inhibiting lithium precipitation of a lithium ion battery, comprising the following steps:
a) Heating the lithium ion battery to a temperature of 40 ℃ to 80 ℃; and
b) Aging the lithium ion battery at the temperature of step a) for 10 hours to 100 hours.
The lithium ion battery may be a battery in any state, and particularly a battery that is returned to the factory for maintenance through use. The lithium ion battery is heated to a temperature of 40 ℃ to 80 ℃ by any suitable means, for example, by an oven, such as a thermostatted oven. When the heating temperature is lower than 40 ℃, the effect of inhibiting the growth of lithium dendrites is not obvious; when the temperature is higher than 80 ℃, the chain exothermic reaction is easily initiated inside the battery, and the thermal runaway of the battery core is caused. Excessive heating temperatures must be prevented, for which reason it is advantageous to control the heating rate to 10 ℃ per hour or less, alternatively 5 ℃ per hour or less. After the lithium ion battery is heated to a predetermined temperature or temperature range, it may be maintained at the temperature or temperature range by a thermostat and aged for 10 to 100 hours. The aging time can be specifically adjusted according to the actual situation of the lithium ion battery. When the aging time is less than 10 hours, the effect of inhibiting the growth of lithium dendrites is insufficient; when the aging time is more than 100 hours, the improvement of the effect of inhibiting the growth of lithium dendrites is significantly reduced, and thus, too long aging time is uneconomical.
Without being bound by any theory, the inventors believe that during high temperature aging of lithium ion batteries by the above method, inevitably precipitated lithium dendrites react more readily with the electrolyte at elevated temperatures, causing a portion of the formed lithium dendrites to thermally "melt". Meanwhile, as the lithium dendrites react with the electrolyte in various complex types, a passivation layer is gradually formed on the surface of the precipitated lithium dendrites. The passivation layer has a low specific surface area, which in turn reduces the reaction rate of lithium dendrites with the electrolyte, so that a chain exothermic reaction does not occur inside the battery, and thermal runaway inside the battery is substantially prevented. The passivation layer gradually thickens as the aging process continues to form, so that lithium ions are difficult to deposit and separate out on the surface of the passivation layer in the form of metallic lithium, thereby inhibiting further growth of lithium dendrites.
In some embodiments, the method comprises in step a) heating the lithium ion battery to a temperature of 45 ℃ to 70 ℃, optionally to a temperature of 55 ℃ to 65 ℃. It has been found that by further selecting a specific heating temperature range, an optimal effect of suppressing the growth of lithium dendrites can be obtained. A higher inhibition effect can be achieved in the temperature range of 55 ℃ to 65 ℃ compared to a lower temperature. The risk of thermal runaway can be further reduced in the temperature range of 55 ℃ to 65 ℃ compared to higher temperatures, such as above 70 ℃. By selecting a specific temperature range for aging, the technical effect of suppressing lithium precipitation can be further improved. The technical effect of suppressing lithium precipitation can be determined by, for example, measuring the magnitude of the short-circuit resistance of a tailored directional lithium-precipitating cell device, the details of which will be described in detail in the examples below.
In some embodiments, the method comprises, in step b), aging the lithium ion battery at the temperature of step a) for 40 hours to 70 hours. As above, the choice of the aging time has a substantial impact on the technical effect of inhibiting lithium precipitation. When the aging time is less than 40 hours, the technical effect of inhibiting lithium precipitation by the method is not fully exerted; when the aging time is longer than 70 hours, the effect of suppressing lithium precipitation is gradually saturated, and although the effect of suppressing lithium precipitation is still sustained, a longer aging time is generally uneconomical in view of high-temperature energy consumption, time, processing throughput, and the like. By specific selection of the aging time, the effect of suppressing the growth of lithium dendrites can be further optimized. In some embodiments, the aging in step b) is accomplished by standing at the above temperature. Obviously, the ageing process may also be carried out by other means than standing, for example by uniformly rotating in a heating device to cause uniform heating.
In some embodiments, in step b), the temperature of aging is kept constant over time or varies in a gradient form over time. By means of an adjustable temperature gradient, the effect of suppressing lithium precipitation can be more effectively adjusted. For example, in one practical heating process, the lithium ion battery to be treated may be heated to 60 ℃ at a constant rate of heating of 5 ℃ per hour and maintained at that temperature for aging for 60 hours. Alternatively, the lithium ion battery to be treated may be rapidly heated to 50 ℃ and aged for 20 hours at a heating rate of 10 ℃ per hour, then the lithium ion battery is warmed up from 50 ℃ to 60 ℃ and aged at this temperature for 20 hours at a heating rate of 5 ℃ per hour, and finally the lithium ion battery is warmed up from 60 ℃ to 70 ℃ and aged at this temperature for 20 hours at a heating rate of 5 ℃ per hour. The gradient heating mode can provide more flexible treatment means to correspond to lithium ion batteries in different lithium separation states.
In some embodiments, the method further comprises the steps of: before heating, the lithium ion battery is disassembled and reassembled, and the discharge capacity is measured to judge the lithium precipitation amount of the negative pole piece of the lithium ion battery. In some embodiments, the method further comprises the steps of: and adjusting the heating temperature and aging time according to the lithium precipitation amount of the negative electrode plate of the lithium ion battery. By setting the aging procedure for a specific lithium amount of the lithium battery, it is possible to improve the efficiency of suppressing lithium precipitation, reduce energy consumption, and reduce the risk of thermal runaway. In some embodiments, the lithium ion battery is a battery that is returned to service after use. For the lithium ion battery in the application, the lithium ion battery has different lithium precipitation states at different stages. The method of the application can generate a technical effect of substantially inhibiting the growth of lithium dendrite for the lithium-ion battery in the lithium-ion battery lithium precipitation state in the whole life cycle. However, for lithium ion batteries having different lithium precipitation states, the actual lithium precipitation amount can be determined by analysis before high-temperature aging treatment, and then the aging temperature and time can be set in a targeted manner, so that the growth of lithium dendrites in the lithium ion battery can be controlled more accurately. The analysis and judgment of the lithium precipitation amount of the lithium ion battery can be performed by the following modes: standing the battery at normal temperature, then performing charge-discharge cycle, and recording the final discharge capacity C1; fully standing the battery at a low temperature and performing high-rate discharge; then, after the battery is kept stand at normal temperature, the battery is disassembled, and the positive pole piece, the electrolyte and the isolating film are taken out; assembling the positive electrode plate, electrolyte, the isolating film and the lithium-filled negative electrode into a new battery; the new battery is discharged after being stood at normal temperature, and the discharge capacity C2 at the moment is recorded; the ratio C2/C1 of the discharge capacities of the front and rear two times is calculated as the lithium precipitation amount of the lithium ion battery. By setting different high-temperature aging parameters, such as heating temperature, aging time, gradient heating, etc., for lithium ion batteries having different lithium precipitation amounts, a more accurate lithium precipitation inhibition effect can be achieved.
In some embodiments, the lithium precipitation is the precipitation and growth of lithium dendrites. After the aging treatment, the surface of the lithium dendrites is passivated. The surface of the passivated lithium dendrite is provided with a passivation layer which prevents further reaction between the lithium dendrite and the electrolyte, and further lithium ions are difficult to continuously separate out on the surface of the formed lithium dendrite, so that the growth of the lithium dendrite is inhibited.
In some embodiments, the methods of the present application further comprise charging the lithium ion battery and allowing it to stand until its internal resistance remains in a steady state prior to heating. This step determines the starting point of the heat aging operation, and the resistance value at this time is also a reference for evaluating the technical effect of inhibiting the growth of lithium dendrites.
In some embodiments, the lithium ion battery is not charged or discharged in steps a) and b). In some embodiments, steps a) and b) are performed at atmospheric pressure. The method is different from the formation treatment of the assembled lithium ion battery, so that the lithium ion battery does not need to be charged and discharged. In particular, the process of the present application need not be carried out under high pressure or evacuated conditions nor under an inert atmosphere such as nitrogen. The method of the application does not need special operation conditions, so that the method has the advantages of convenient operation and low cost.
The composition and structure of the lithium ion battery will be described in detail.
In general, a lithium ion battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece to play a role in isolation. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate.
[ electrolyte ]
The detection device according to the application comprises an electrolyte. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The electrolyte includes an electrolyte salt and a solvent.
In the present application, the electrolyte salt may beCommon electrolyte salts in lithium ion batteries, such as lithium salts, include those that may be the above-described lithium salts as high heat stability salts, lithium salts as low impedance additives, or lithium salts that inhibit corrosion of aluminum foil. As an example, the electrolyte salt may be selected from LiPF 6 Lithium hexafluorophosphate, liBF 4 Lithium tetrafluoroborate, liAsF 6 (lithium hexafluoroarsenate), liFeSI (lithium difluorosulfimide), liTFSI (lithium bistrifluorosulfimide), liTFS (lithium trifluoromethane sulfonate), liDFOB (lithium difluorooxalato borate), liPO 2 F 2 (lithium difluorophosphate), liDFOP (lithium difluorodioxalate phosphate), liSO 3 F (lithium fluorosulfonate), NDFOP (difluorooxalate), li 2 F(SO 2 N) 2 SO 2 F、KFSI、CsFSI、Ba(FSI) 2 LiSO 2 NSO 2 CH 2 CH 2 CF 3 More than one of them.
The kind of the solvent is not particularly limited and may be selected according to actual demands. In some embodiments, the solvent is a non-aqueous solvent. Alternatively, the solvent may comprise one or more of a chain carbonate, a cyclic carbonate, a carboxylic acid ester. In some embodiments, the solvent may be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), butylene Carbonate (BC), fluoroethylene carbonate (FEC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), tetrahydrofuran, sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, other additives may also be optionally included in the electrolyte. For example, the additives may include negative electrode film-forming additives, or may include positive electrode film-forming additives, or may include additives that improve certain properties of the battery, such as additives that improve the overcharge properties of the battery, additives that improve the high temperature properties of the battery, additives that improve the low temperature properties of the battery, and the like. As an example, the additive is selected from at least one of a cyclic carbonate compound containing an unsaturated bond, a halogen-substituted cyclic carbonate compound, a sulfate compound, a sulfite compound, a sultone compound, a disulfonic acid compound, a nitrile compound, an aromatic compound, an isocyanate compound, a phosphazene compound, a cyclic anhydride compound, a phosphite compound, a phosphate compound, a borate compound, and a carboxylate compound.
[ Positive electrode sheet ]
The positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material and a conductive agent.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode active material layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
The positive current collector may be a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (e.g., aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
The positive electrode active material layer disposed on the surface of the positive electrode current collector includes a positive electrode active material. The positive electrode active material used in the present application may have any conventional positive electrode active material used in secondary batteries. In some embodiments, the positive electrode active material may include one or more selected from lithium transition metal oxides, olivine structured lithium-containing phosphates, and their respective modified compounds. Examples of the lithium transition metal oxide may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, and modified compounds thereof. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate-carbon composites, lithium manganese phosphate-carbon composites, lithium manganese phosphate-iron, lithium manganese phosphate-carbon composites, and modified compounds thereof. These materials are commercially available. The surface of the positive electrode active material may be coated with carbon.
The positive electrode active material layer optionally includes a conductive agent. However, the kind of the conductive agent is not particularly limited, and one skilled in the art may select according to actual needs. As an example, the conductive agent for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
The positive electrode active material layer may further optionally include a binder. As an example, the binder may be one or more of styrene-butadiene rubber (SBR), aqueous acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).
The positive electrode sheet may be prepared according to methods known in the art. As an example, the carbon-coated positive electrode active material, the conductive agent, and the binder may be dispersed in a solvent, such as N-methylpyrrolidone (NMP), to form a uniform positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ negative electrode sheet ]
The negative electrode tab includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer including a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode material layer is provided on either one or both of the two surfaces opposing the anode current collector.
In the electrode assembly of the present application, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (e.g., copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In the electrode assembly of the present application, the anode material layer generally contains an anode active material, and optionally a binder, an optional conductive agent, and other optional auxiliary agents, and is generally formed by coating and drying an anode slurry. The negative electrode slurry coating is generally formed by dispersing a negative electrode active material, an optional conductive agent, a binder, and the like in a solvent and stirring uniformly. The solvent may be N-methylpyrrolidone (NMP) or deionized water.
The specific kind of the negative electrode active material is not limited, and an active material known in the art to be capable of being used for a negative electrode of a lithium ion secondary battery may be used, and those skilled in the art may select according to actual demands. As an example, the negative electrode active material may be selected from one or more of graphite, soft carbon, hard carbon, mesophase carbon microspheres, carbon fibers, carbon nanotubes, elemental silicon, silicon oxygen compounds, silicon carbon composites, lithium titanate.
As an example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
As an example, the binder may be selected from one or more of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
Other optional adjuvants are, for example, thickeners such as sodium carboxymethylcellulose (CMC-Na), etc.
[ isolation Membrane ]
The electrode assembly using the electrolyte further includes a separator. The isolating film is arranged between the positive pole piece and the negative pole piece to play a role in isolation. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used. In some embodiments, the material of the isolation film may be selected from more than one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the electrode assembly may include an overwrap. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer packaging of the electrode assembly may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The outer package of the electrode assembly may also be a pouch, such as a pouch-type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
The shape of the lithium ion battery is not particularly limited, and may be cylindrical, square, or any other shape.
Fig. 1 is a side view of a lithium ion battery of a tailored directed lithium-ion battery used for detecting a short-circuit resistance according to an embodiment of the present application, in which an internal resistance meter connecting a negative electrode tab with a copper foil electrode is not shown. The electrode comprises a negative electrode plate 2, a positive electrode plate 3, a copper foil electrode 1, a separation film 4, an insulating part 5 and insulating glue 6. The electrolyte is filled between the negative electrode sheet and the positive electrode sheet, and is not particularly marked.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. Unless otherwise indicated, all experimental steps were carried out at normal pressure.
Preparation of a specially-made lithium ion battery for directional lithium separation:
the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Acetylene black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 95.5:2.5: and 2, fully stirring and uniformly mixing the mixture in an N-methyl pyrrolidone solvent system, coating the mixture on an aluminum foil, drying and cold pressing the aluminum foil, and obtaining the positive electrode plate. Artificial graphite as a negative electrode active material, acetylene black as a conductive agent, styrene-butadiene rubber (SBR) as a binder and sodium carboxymethylcellulose (CMC) as a thickener according to a mass ratio of 96.5:1.5:1: and 1, fully stirring and uniformly mixing the materials in a deionized water solvent system, coating the materials on a copper foil, drying and cold pressing the materials, and obtaining the negative electrode plate. Using conventional 1mol/LLiPF 6 (ethylene carbonate (EC) +methylethyl carbonate (EMC) +dimethyl carbonate (DMC) =1:1:1 (V/V)) as an electrolyte. The thickness of the copper foil electrode is basically the same as that of the negative electrode plate. A polypropylene film was used as a separator.
The manufacturing process of the lithium ion battery is carried out in a drying room, wherein the side surfaces of the non-end surfaces of the copper foil electrode are respectively coated with PET insulating glue with the thickness of 20 mu m in an insulating way. The copper foil electrode was sandwiched by 200 μm thick mylar (i.e., PET mylar) films as insulation portions on both sides of the copper foil electrode to be fixed at a position horizontally opposite to the negative electrode tab. The distance between the end face of the copper foil electrode and the end face of the negative electrode plate is 1.2mm. The negative electrode plate is 0.8mm longer than the positive electrode plate on one side of the copper foil electrode. The negative electrode sheet, the separator, the positive electrode sheet and the copper foil electrode were placed in the order shown in fig. 1, and then wound to obtain an electrode assembly. The electrode assembly is placed in a battery case, dried, and then an electrolyte is injected. The copper foil electrode is connected with the tab of the negative electrode plate through an internal resistance meter solar BT3562 arranged in situ.
The detection mechanism is as follows: in the charging process of the special lithium ion battery for directional lithium precipitation, as the negative electrode plate is longer than the positive electrode plate by a small section on one side, lithium ions are relatively concentrated on the end face of the negative electrode plate on the side and precipitate to form lithium dendrites in the charging process. As the charging process proceeds, lithium dendrites continue to grow and extend from the side face of the negative electrode tab toward the end face of the copper foil electrode disposed substantially horizontally and opposite thereto. And connecting the copper foil electrode and the negative electrode plate through an internal resistance meter, and continuously collecting the resistance value between the copper foil electrode and the negative electrode plate. In the process of continuously growing and extending the lithium dendrite, along with the fact that the tip of the lithium dendrite is continuously close to the end face of the copper foil electrode, the resistance value between the copper foil electrode and the negative electrode piece collected by the internal resistance meter theoretically tends to be continuously reduced. When the lithium dendrite finally extends to the end face of the copper foil electrode and is overlapped with the end face of the copper foil electrode, a short circuit is formed between the copper foil electrode and the negative electrode plate. At this time, the resistance value between the copper foil electrode and the negative electrode piece collected by the internal resistance meter will show a drastic decrease, and theoretically even decrease to be close to zero. Of course, since lithium dendrites undergo various side reactions with the electrolyte during actual charging, a passivation layer of a certain thickness is generated on the surface thereof. The passivation layer can enable the resistance value between the copper foil electrode and the negative electrode piece acquired by the internal resistance meter to be in a lower resistance value range higher than zero. When left standing at normal temperature for a long time under this condition, the resistance value eventually stabilizes at a lower value.
The resistance value between the copper foil electrode and the negative electrode plate is measured by using an internal resistance meter, so that the precipitation condition of lithium ions on the end face of the negative electrode plate facing the copper foil electrode, namely the growth process of lithium dendrites, can be detected in real time. The more the lithium dendrite grows, the closer the tip of the lithium dendrite is to the end face of the copper foil electrode opposite to the negative electrode piece, and the resistance value between the copper foil electrode and the negative electrode piece acquired by the internal resistance meter is reduced more and more. By plotting the resistance value between the copper foil electrode and the negative electrode piece acquired by the internal resistance meter and the corresponding time, the function relation of the change of the resistance value along with the time can be obtained, and the function relation reflects the precipitation, growth and passivation states of lithium dendrites along with the time.
However, it should be emphasized that the specific lithium ion battery for directional lithium precipitation is only used for intuitively representing the inhibiting effect of temperature and time on the lithium precipitation phenomenon in the aging process, and is shown in the form of the resistance value in the short circuit, so as to facilitate qualitative and quantitative analysis. It will be appreciated that the method of the present application is applicable to other conventional lithium ion batteries, which also have similar effects of suppressing lithium precipitation.
Example 1
The specially prepared lithium ion battery with directional lithium separation is formed by adopting a 0.1C charging multiplying power. After the formation is completed, the device is charged to 4.25V by constant current charging with a charging rate of 0.33C, and is charged at constant voltage after reaching a cut-off voltage, and the device is at normal temperature (25 ℃). After the internal resistance of the lithium ion battery is stable, transferring the lithium ion battery to an oven with the temperature of 45 ℃ for standing, and observing the resistance change between the copper foil electrode and the negative electrode piece measured by the internal resistance meter.
Examples 2 to 10 and comparative examples are also specific examples in which the standing temperature and time were changed, and the other methods and detection procedures were the same as in example 1 except for the parameters of table 1. The specific experimental conditions are set forth in table 1.
Table 1: method parameters of examples 1-10 and comparative examples 1-3
| Group of | Rest temperature | Standing time |
| Example 1 | 45℃ | 12h |
| Example 2 | 45℃ | 24h |
| Example 3 | 45℃ | 36h |
| Example 4 | 45℃ | 48h |
| Example 5 | 60℃ | 12h |
| Example 6 | 60℃ | 24h |
| Example 7 | 60℃ | 36h |
| Example 8 | 60℃ | 48h |
| Example 9 | 70℃ | 24h |
| Example 10 | 70℃ | 48h |
| Comparative example 1 | 25℃ | 0h |
| Comparative example 2 | 25℃ | 0h |
| Comparative example 3 | 25℃ | 0h |
The lithium ion batteries of examples 1 to 10 and comparative examples 1 to 3 were respectively subjected to short-circuit internal resistance tests, and the test results are shown in table 2. Among them, the same lithium ion battery 1 was used for the test procedures of comparative example 1 and examples 1 to 4, the same lithium ion battery 2 was used for the test procedures of comparative example 2 and examples 5 to 8, and the same lithium ion battery 3 was used for the test procedures of comparative example 3 and examples 9 to 10. The components of the lithium ion batteries 1-3 are the same, and only due to the deviation of the actual operation process (for example, the lithium precipitation conditions of different batteries are different, such as different length differences of the positive electrode and the negative electrode or different distances between the end face of the negative electrode and the copper foil electrode, the initial standing time required for achieving stable resistance is different), the stable internal resistance detected by the prepared lithium ion battery at 25 ℃ is different. For example, for the lithium ion battery 1, after it was subjected to the above charging process, its stable internal resistance value, i.e., the short circuit internal resistance of comparative example 1, was detected while being maintained at 25 ℃. The device 1 was then warmed to 45 ℃ and allowed to stand at that temperature for 12h, 24h, 36h and 48h, respectively, and then the internal resistance values, i.e., the short circuit internal resistances of examples 1, 2, 3 and 4, respectively, were measured. The measurement of the internal resistance value is real-time, i.e., the temperature at the time of measurement is the temperature at rest. The same applies to other embodiments and lithium ion battery types. Table 2 below summarizes the short circuit internal resistance test results of examples 1-10 and comparative examples 1-3.
Table 2: short-circuit internal resistance test results of examples 1 to 10 and comparative examples 1 to 3
| Group of | Short circuit internal resistance (omega) | Resistance value increase multiple |
| Example 1 | 186 | 5.6 |
| Example 2 | 550 | 16.7 |
| Example 3 | 584 | 17.7 |
| Example 4 | 606 | 18.4 |
| Example 5 | 400 | 16.7 |
| Example 6 | 650 | 27.1 |
| Example 7 | 720 | 30 |
| Example 8 | 780 | 32.5 |
| Example 9 | 510 | 51 |
| Example 10 | 740 | 74 |
| Comparative example 1 | 33 | / |
| Comparative example 2 | 24 | / |
| Comparative example 3 | 10 | / |
As can be seen from table 2, the high-temperature stationary aging method of the present application has a remarkable inhibitory effect on lithium dendrite growth of lithium ion batteries. For example, for comparative example 2 and examples 5-8, the same lithium ion battery was used. The stable internal resistance measured at a temperature of 25℃and a time t (time) of 0h was the resistance value 24Ω of comparative example 2. When the temperature is increased from 25 ℃ to 60 ℃, the measured internal resistance value after 12 hours is 400 omega, and compared with the internal resistance value before high-temperature aging, the internal resistance value is increased to 16.7 times of the original value; the internal resistance value measured after 24 hours at this temperature was 650 Ω, which was 27.1 times higher than the internal resistance value before high-temperature aging; the internal resistance value measured after 36h at this temperature is 720 Ω, which is 30 times higher than the internal resistance value before high-temperature aging; and the internal resistance value measured after 48 hours at this temperature was 780 Ω, which was 32.5 times higher than that before high-temperature aging. Reference is also made to the curves shown in fig. 2 of the present application for specific variations. It can be seen that the increase in temperature and the increase in aging time both significantly increase the resistance of the short-circuit internal resistance, indicating that the growth of lithium dendrites is significantly inhibited while the surface thereof has been passivated to a considerable extent. It can also be seen that as the aging time further increases, the magnitude of the increase in the internal resistance value gradually decreases, which means that the improvement effect obtained by continuing to greatly extend the aging time will gradually decrease.
For other examples, similar effects to aging at 60℃were also observed at 45℃as well as at 70 ℃. Of course, the higher the temperature, the higher the multiple of the increase in the internal resistance value thereof within the same time, meaning that the effect of suppressing the growth of lithium dendrites is more remarkable. However, higher temperatures also mean that the risk of thermal runaway inside the battery at high temperatures is also higher.
While the application has been described with reference to an exemplary embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the application. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (13)
1. A method for inhibiting lithium ion battery lithium precipitation, comprising the steps of:
a) Heating the lithium ion battery to a temperature of 40 ℃ to 80 ℃; and
b) Aging the lithium ion battery at the temperature of step a) for 10 hours to 100 hours.
2. The method according to claim 1, wherein in step a) the lithium ion battery is heated to a temperature of 45 ℃ to 70 ℃, optionally to a temperature of 55 ℃ to 65 ℃.
3. The method according to claim 1 or 2, wherein in step b) the lithium ion battery is aged at the temperature of step a) for 40 to 70 hours.
4. A method according to any one of claims 1 to 3, wherein the ageing in step b) is accomplished by standing at said temperature.
5. The method according to any one of claims 1 to 4, wherein the temperature of aging in step b) is kept constant over time or varies in a gradient form over time.
6. The method according to any one of claims 1 to 4, further comprising the step of:
before heating, the lithium ion battery is disassembled and reassembled, and the discharge capacity is measured to judge the lithium precipitation amount of the negative pole piece of the lithium ion battery.
7. The method of claim 5, further comprising the step of:
and adjusting the heating temperature and aging time according to the lithium precipitation amount of the negative electrode plate of the lithium ion battery.
8. The method according to any one of claims 1 to 7, wherein the lithium ion battery is a battery that is returned to factory for maintenance through use.
9. The method of any one of claims 1 to 8, wherein the lithium precipitation is precipitation and growth of lithium dendrites.
10. The method of claim 9, wherein after the aging treatment, the surface of the lithium dendrites is passivated.
11. The method of any one of claims 1 to 10, further comprising charging and standing the lithium ion battery until its internal resistance value remains in a steady state prior to heating.
12. The method according to any one of claims 1 to 11, wherein the lithium ion battery is not charged or discharged in the steps a) and b).
13. The method according to any one of claims 1 to 11, wherein the steps a) and b) are performed at atmospheric pressure.
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| PCT/CN2023/078629 WO2023207307A1 (en) | 2022-04-26 | 2023-02-28 | Method for inhibiting lithium precipitation of lithium ion battery |
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